PL:1 THE APPLICATION OF PHOTOREDOX CATALYSIS TO NEW

RUSSIAN ACADEMY OF SCIENCES (RAS)
DIVISION OF CHEMISTRY AND MATERIAL SCIENCES, RAS
RUSSIAN FOUNDATION FOR BASIC RESEARCH
SCIENTIFIC COUNCIL ON ORGANIC CHEMISTRY, RAS
ND ZELINSKY INSTITUTE OF ORGANIC CHEMISTRY, RAS
International Conference
Molecular Complexity in
Modern Chemistry
MCMC-2014
BOOK OF ABSTRACTS
September 13-19, 2014
Moscow, Russia
International Advisory Committee
H. Alper, University of Ottawa, Canada
D. Astruc, University of Bordeaux, France
J. Dupont, Institute of Chemistry, Brazil
P. J. Dyson, EPFL, Switzerland
R. G. Finke, Colorado State University, USA
G. C. Fu, California Institute of Technology, USA
A. Furstner, Max Planck Institut fur Kohlenforschung, Germany
V. K. Jain, Bhabha Research Centre, India
C.W. Jones, Georgia Institute of Technology , USA
P.-H. Leung, Nanyang Technological University, Singapore
C. Najera, Universidad de Alicante, Spain
E.-i. Negishi, Purdue University, USA
L. A. Oro, University of Zaragoza-CSIC, Spain
R. Poli, Institut National Polytechnique, France
V. Snieckus, Queen's University, Canada
M. Taillefer, Institut Charles Gerhardt, France
A. M. Trzeciak, University of Wroclaw, Poland
Y. Yamamoto, Tohoku University, Japan
Local Organizing Committee
ND Zelinsky Institute of Organic Chemistry, RAS
M. P. Egorov, Chairman
V. P. Ananikov, Vice-chairman
A. D. Dilman
A. M. Sakharov
A. Y. Stakheev
A.M. Starosotnikov
A. O. Terentev
O. V. Turova
S. G. Zlotin
National Advisory Committee
G. A. Abakumov, N. Novgorod
I. P. Beletskaya, Moscow
Y. N. Bubnov, Moscow
V. N. Charushin, Ekaterinburg
O. N. Chupakhin, Ekaterinburg
A. I. Konovalov, Kazan
V. V. Lunin, Moscow
V. I. Minkin, Rostov
O. M. Nefedov, Moscow
V. N. Parmon, Novosibirsk
O. G. Syniashin, Kazan
V. A. Tartakovsky, Moscow
B. A. Trofimov, Irkutsk
M. S. Yunusov, Ufa
N. S. Zefirov, Moscow
Index
Plenary Lectures ........................................................................................... 7
Invited Lectures .......................................................................................... 22
Oral Communications ................................................................................. 60
Posters ....................................................................................................... 110
Authors Index ........................................................................................... 326
Plenary Lectures
7
8
PL1
THE APPLICATION OF PHOTOREDOX CATALYSIS TO NEW
TRANSFORMATIONS IN CHEMICAL SYNTHESIS
D.W.C. MacMillan
Merck Center for Catalysis, Princeton University,Princeton, NJ 08544
This lecture will discuss the advent and development of new concepts in chemical synthesis,
specifically the combination of photoredox catalysis with organic catalysis. This new approach to
“synergistic catalysis” will demonstrate that multiple yet separate catalytic cycles can be aligned to
generate activated intermediates that rapidly combine with each other, thereby allowing new
approaches to enantioselective C–C and C-heteroatom bond formation.
We will also introduce an approach to the discovery of new chemical reactions that we term
accelerated serendipity. Accidental or ‘serendipitous’ discoveries have led to some of the most
important breakthroughs in scientific history, many of which have directly affected human life.
Given our overarching goal of developing fundamentally new and useful chemical transformations
using catalysis and by acknowledging the tremendous impact of serendipity in scientific discovery,
we questioned whether this phenomenon could be forced or simulated and therefore employed as a
tool for reaction discovery.
In this presentation, we will describe several new transformations that have been discovered via
“accelerated serendipity” that we expect will find widespread adoption throughout the field of
chemical synthesis. Moreover, we will further describe how mechanistic understanding of these
processes has led to the design of a valuable, new yet fundamental chemical transformation.
Acknowledgements
Financial support was provided by NIHGMS (R01 01 GM093213-01) and kind gifts from Merck,
Amgen, and Abbott.
9
PL2
GOLD CATALYSIS 2.0
A.S.K. Hashmi
Organisch-Chemisches Institut, Fakultät für Chemie und Geowissenschaften, Universität
Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Homogeneous catalysis by gold has developed to an important sector of catalysis research.1
Initially, efforts in methodology development clearly dominated, in the last years also an increasing
number of applications in synthesis has been reported.2,3 Efforts to understand the basic mechanism
of these reactions continuously accompanied the field.4
For twelve years most of the reactions followed simple reaction mechanisms basing on the
interaction of one gold centre in a gold complex or organogold compound with the substrate
molecule. In most of these reactions vinylgold or alkylgold intermediates are involved, sometimes
also gold carbenoids.
Now an entirely new family of reactions, basing on the activation of the organic substrates by two
gold complexes at the same time (one -coordinated, the other -coordinated), has been discovered.
These open up entirely new synthetic possibilities and follow quite complex mechanisms. These
mechanisms, which are new to the field of organometallic chemistry, will be discussed in detail.
Some of the new reactions even allow positional selective C,H activations of alkyl side chains, as
exemplified below.
The presentation will also contain results from computational chemistry.
References:
1. A. S. K. Hashmi, Chem. Rev. 2007, 107, 3180-3211.
2. A. S. K. Hashmi, M. Rudolph, Chem. Soc. Rev. 2008, 37, 1766-1775.
3. M. Rudolph, A. S. K. Hashmi, Chem. Soc. Rev. 2012, 41, 2448-2462.
4. A. S. K. Hashmi, Angew. Chem. Int. Ed. 2010, 49, 5232-5241.
10
PL3
HOW MUCH CATALYST DO WE NEED?
C. Bolm
Institute of Organic Chemistry, RWTH Aachen University, 52056 Aachen, Germany
Various C-N-, C-O-, and C-C-bond forming reactions leading to cross coupling-type products can
be performed without transition metals. In this presentation we will discuss cyclizations affording
benzimidazol-2-ones1 and indazoles2 (eqs. 1 and 2, respectively). Photochemical initiations (eq. 3)
led us to other directions.3,4
R2
R2
H
N
N
R1
X
N
KOH/DMSO
R3
O
40 °C, 24 h
O
R3
X = I, Br (Cl, F)
R2
R2
diamine/K2CO3
N
R1
X
HN
R3
R1
N
R3
X = I, Br
O
TMS
hn
CH2Cl2, RT
O
(eq. 2)
N
toluene, RT, 2.5 h
O
R1
(eq. 1)
N
R1
TMS
R2
R1
(eq. 3)
O
R2
Finally we will present mechanochemical activations in ball mills that allow reducing the catalyst
loadings in asymmetric organocatalyses.5-7
References:
1. a) Yuan, Y.; Thomé, I.; Kim, S. H.; Chen, D.; Beyer, A.; Bonnamour, J.; Zuidema, E.; Chang,
S.; Bolm, C. Adv. Synth. Catal. 2010, 352, 2892. b) Beyer, A.; Reucher, C. M. M.; Bolm, C.
Org. Lett. 2011, 13, 2876. c) Thomé, I.; Bolm, C. Org. Lett. 2012, 14, 1892. d) Beyer, A.;
Buendia, J.; Bolm, C. Org. Lett. 2012, 14, 3948. e) Baars, H.; Beyer, A.: Kohlhepp, S. V.; Bolm,
C. Org. Lett. 2014, 16, 536.
2. Thomé, I.; Besson, C.; Kleine, T.; Bolm, C. Angew. Chem. Int. Ed. 2013, 52, 7509.
3. a) Zhang, H.-J.; Becker, P. Huang, H.; Pirwerdjan, R.; Pan, F.-F.; Bolm, C. Adv. Synth. Catal.
2012, 354, 2157. b) Becker, P.; Priebbenow, D. L.; Zhang, H.-J.; Pirwerdjan, R.; Bolm, C. J.
Org. Chem. 2014, 79, 814. c) Becker, P.; Priebbenow, D. L.; Pirwerdjan, R.; Bolm, C. Angew.
Chem. Int. Ed. 2014, 53, 269.
4. For a photochemical activation in a metal catalysis, see: Bizet, V.; Buglioni, L.; Bolm, C.
Angew. Chem. Int. Ed. DOI: 10.1002/anie.201310790.
5. a) Jörres, M.; Mersmann, S.; Raabe, G.; Bolm, C. Green Chem. 2013, 15, 612. See also in: b)
Kleine, T.; Buendia, J.; Bolm, C. Green Chem. 2013, 15, 160.
6. For a video, see: http://www.beilstein.tv/tvpost/asymmetric-organocatalysis-in-a-ball-mill/
7. For a general overview, see: James, S. L.; Collier, P.; Parkin, I.; Hyett, G.; Braga, D.; Maini, L.;
Jones, B.; Friscic, T.; Bolm, C.; Krebs, A.; Mack, J.; Waddell, D. C.; Shearouse, W. C.; Orpen,
G.; Adams,C.; Steed, J. W.; Harris, K. D. M. Chem. Soc. Rev. 2012, 41, 413.
11
PL4
“MOLECULAR METATHESIS CATALYSTS” AT THE DAWN OF
INDUSTRIAL IMPLEMENTATION
D.E. Fogg
University of Ottawa
Ruthenium-catalyzed olefin metathesis has enormous potential for impact on the chemical
enterprise, in sectors ranging from pharma to specialty polymers and “green” feedstocks.
Phosphine-free metathesis catalysts, particularly those of the Hoveyda type (HII, see Figure 1),
occupy a position of increasing prominence. In one of the most high-profile current applications of
metathesis chemistry, transformation of seed oils into functionalized olefins, HII significantly outperforms the benchmark Grubbs catalyst GII, [1,2] despite the fact that the two catalysts generate a
common active species (A). Reports from pharma R&D indicate that HII also offers superior
performance in some demanding RCM applications (RCM = ring-closing metathesis).[3] As these
and closely related molecular metathesis catalysts enter deployment in process chemistry,
understanding the mechanistic basis of their performance takes on added importance.
We will discuss potential contributors to the improved productivity of HII: the absence of free
PCy3, the presence of the styrenyl ether ligand, and operation of HII via interchange-associative
pathways. The relevance of each of these factors will be considered in the context of demanding
ring-closing and cross-metathesis reactions..
Figure 1. Molecular structure of an organometallic product.
References
[1] Miao, X.; Fischmeister, C.; Dixneuf, P. H.; Bruneau, C.; Dubois, J. L.; Couturier, J. L. Green
Chem. 2012, 14, 2179-2183.
[2] Biermann, U.; Bornscheuer, U.; Meier, M. A. R.; Metzger, J. O.; Schafer, H. J. Angew. Chem.
Int. Ed. 2011, 50, 3854–3871.
[3] van Lierop, B. J.; Lummiss, J. A. M.; Fogg, D. E., Ring-Closing Metathesis: A How-To Guide.
In Olefin Metathesis: Theory and Practice, Grela, K., Ed. Wiley: Weinheim, 2014.
12
PL5
REDUCTIONS WITH ORGANIC REAGENTS — THE ELECTRON AS A
CATALYST!
A. Studer
WWU Muenster, Chemistry, Germany
In the lecture reduction processes for generation of various radicals using different organic reagents
will be presented. Reactions are generally conducted using stoichiometric SET-reagents. However,
also some catalytic variants will be presented. In the presentation radical perfluoroalkylations and
azidations will be addressed. Moreover, the concept of using the electron as a catalyst will be
discussed and some examples provided.
13
PL6
NANOELECTRONICS: MOLECULAR METAL WIRES AND RELATED
MOLECULAR MATERIALS
S.M. Peng
Department of Chemistry, National Taiwan University, Taipei, Taiwan
We have designed a series of new ligands such as oligo-α-pyridylamines, and used them to
construct an unique class of quadruple helix of metal strings. This achievement leads to a new
direction to the application of molecular wires in the nanoelectronics.
The outline is as follows:
I. Linear Metal String Complexes (1)
◎ Synthesis, Structure, Bonding
II. Potential Application as Molecular Metal Wires & Molecular Switches (2)
◎ STM-bj Study on the Conductivity of Metal Strings
◎ Comparative Study on the I-V Characterisics (Theory V.S. Experiment)
III. Tuning of the Metal Strings (3-9)
◎ Naphthyridyl Amino Ligands: Low Oxidation Mixed Metal Strings
◎ Asymmetrical Ligands: Toward Molecular Rectifier
◎ Heteronuclear Metal String Complexes
◎ Chiral Quadruple Helixes
IV. Conclusion
X
N
N
N
N
M
M
M
M
N
M
4
X
M = N i, C o , C r
m = 0, 1, 2, 3
X = C l, N C S
m
Fig.1 Metal Strings of Oligo- -pyridylamido Ligands
1. C.-Y. Yeh, C.-C. Wang, Y.-H. Chen and S.-M. Peng, in Redox Systems Under Nano-Space
Control, Ed: T, Hirao, Springer, Germany 2006, Ch. 5.
2. I.-W. P. Chen, M.-D. Fu, W.-H. Tseng, J.-Y. Yu, S.-H. Wu, C.-J. Ku, C.-H. Chen, and S.-M.
Peng, Angew. Chem. Int. Ed. Engl. 2006, 5414.
3. (a) C.-H. Chien, J.-C. Chang, C.-Y. Yeh, G.-H. Lee, J.-M. Fang and S.-M. Peng, Dalton Trans.
2006, 2106. (b) C.-H. Chien, G.-H. Lee, Y. Song and S.-M. Peng, Dalton Trans. 2006, 3249.
4. M.-M. Rohmer, I. P.-C. Liu, J.-C. Lin, M.-J. Chiu, C.-H. Lee, G.-H. Lee, M. Benard, X. Lopez,
S.-M. Peng, Angew. Chem. Int. Ed. Engl. 2007, 46, 3533.
5. I. P.-C. Li, W.-Z. Wang, and S.-M. Peng, Chem. Commun. 2009, 4323-4331.
6. R. H. Ismayilov, W.-Z.Wang, G. H. Lee, C. Y. Yeh, S. A. Hua, Y. Song, M. M. Rohmer, M.
Bénard, S.-M. Peng, Angew. Chem. Int. Ed., 2011, 50, 2045-2048.
7. I. P.-C. Liu, C.-H. Chen, S.-M. Peng, Bull. Jpn. Soc. Coord. Chem., 2012, 59, 1-8.
14
8. M.-C. Cheng, C.-L. Mai, C.-Y. Yeh, G.-H. Lee, S.-M. Peng, Chem. Commun. 2013, 49, 79387940
9. M.-J. Huang, S.-A Hua, M.-D. Fu, G.-C. Huang, C. Yin, C.-H. Ko, C-K. Kuo, C-H. Hsu, G.-H.
Lee, K.-Y. Ho, C.-H. Wang, Y.-W. Yang, I.-C Chen, S.-M. Peng, C.-h. Chen, Chem. Eur. J.
2014, DOI: 10.1002/chem.201400067
15
PL7
NEW CYCLOADDITION STRATEGIES BASED ON STRAINED AND
UNUSUAL MOLECULES
R.L. Danheiser
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 USA
Highly substituted carbocyclic and heterocyclic rings are key structural features in many
biologically significant and commercially important compounds. Although classical synthetic
approaches to such compounds have generally relied on linear substitution strategies, convergent
cycloaddition and annulation strategies have emerged as powerful alternative methods for the
assembly of highly substituted cyclic compounds. The intrinsic convergent nature of cycloaddition
and annulation strategies facilitates the efficient assembly of highly substituted systems that would
have required long, multistep routes using alternative methods.
This talk will focus on the application of strained and unusual molecules as building blocks in
cycloaddition strategies for the construction of complex carbocyclic and heterocyclic compounds.
The synthetic utility of highly unsaturated, conjugated molecules such as vinylketenes, conjugated
enynes, vinylallenes, allenylimines, and iminoacetonitriles will be described, as well as their
application in the total synthesis of natural products.
16
PL8
SILICON TETHER MOTIF IN C-H ACTIVATION REACTIONS
V. Gevorgyan
University of Illinois at Chicago
We have developed a set of new transition metal-catalyzed C-H activation methodologies
employing a silicon-tether motif. These methods feature: (a) use of silyl group as a tether between a
substrate and a reagent, thus transforming intermolecular reaction into intramolecular reaction;1-2
(b) employment of a silicon-tethered directing group, which is traceless or easily convertable into
valuable functionalities;3-8 (c) use of silyl-tethered hydrosilane reagent;9-10 and (d) introduction of
new N/Si-chelation concept that allows for a remote activation of aliphatic C-H bonds.11
The scope of these transformations will be demonstrated and the mechanisms will be discussed.
References
1. Huang C., Gevorgyan V. J. Am. Chem. Soc. 2009, 131, 10844.
2. Huang, C.; Gevorgyan, V. Org. Lett. 2010, 12, 2442.
3. Chernyak N., Dudnik A. S., Huang C., Gevorgyan V. J. Am. Chem. Soc. 2010, 132, 8270.
4. Dudnik A. S., Chernyak N., Huang C., Gevorgyan V. Angew. Chem., Int. Ed. 2010, 49, 8729.
5. Huang C., Chattopadhyay B., Gevorgyan V. J. Am. Chem. Soc. 2011, 133, 12406.
6. Huang C., Ghavtadze N., Chattopadhyay B., Gevorgyan V. J. Am. Chem. Soc. 2011, 133, 17630.
7. Gulevich, A. V.; Melkonyan, F. S.; Sarkar, D.; Gevorgyan, V. J. Am. Chem. Soc. 2012, 134,
5528.
8. Sarkar, D.; Melkonyan, F. S.; Gulevich, A. V.; Gevorgyan, V. Angew. Chem., Int. Ed. 2013, 52,
10800.
9. Kuznetsov, A.; Gevorgyan, V. Org. Lett. 2012, 14, 914.
10. Kuznetsov, A.; Onishi, Y.; Inamoto, Y.; Gevorgyan, V. Org. Lett. 2013, 15, 2498.
11. Ghavtadze, N; Melkonyan, F. S.; Gulevich, A.; Huang, C.; Gevorgyan, V. Nat. Chem. 2014, 6,
122.
17
PL9
WERNER COMPLEXES: A NEW CLASS OF CHIRAL HYDROGEN BOND
DONOR CATALYSTS FOR ENANTIOSELECTIVE ORGANIC REACTIONS
J.A. Gladysz
Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 778423012, USA
Salts of the chiral tris(ethylenediamine)-substituted octahedral trication [Co(en)3]3+, and related
species, have played important historical roles in the development of inorganic chemistry and
stereochemistry.1,2 As Werner described in 1912, the two enantiomers, commonly designated and
, can be separated by crystallization of the diastereomeric tartrate salts. 2 However, despite the low
cost and ready availability of the building blocks, there have been no applications in
enantioselective organic synthesis.
L
H 2N
NH 2 H
2
N
3+
Co
H 2N
NH 2
N
H2
H 2 H 2N
N
3+
Co
NH 2
N
H2
NH 2
D
H 2N
We have found that [Co(en)3]3+ and related cations can be rendered soluble in organic solvents by
using lipophilic anions such as "BArf–".3 Suitably functionalized derivatives act as highly
enantioselective catalysts for a variety of carbon-carbon bond forming reactions. The mechanisms
involve outer sphere activation of the electrophile by hydrogen bonding to the NH moieties. Other
types of metal-containing chiral hydrogen bond donors are also effective, including a chelate of the
CpRuL fragment.
O
NO 2
O
O
MeO
X
10 mol% cat.
OMe
1.2 eq.
O
MeO
OMe
NO 2
Et 3N, acetone
0 °C
X
Ph
Ph
Ph
H 2N
H 2N
Ph
NH 2 H
2
3+ N
Co
N
H
NH 2 2
Ph
2Cl – BAr f–
Ph
H 2N
Ph
L
Ph
H 2N
Ph
Ph
Ph
NH 2 H
2
3+ N
Co
N
H
NH 2 2
H 2N
2BF4– BAr f–
Ph
H 2N
L
Ph
Time Conversion ee
(h)
(%)
(%)
O
Ph
NH 2 H
2
3+ N
Co
N
H
NH 2 2
Ph
Ph
Time Conversion ee
(h)
(%)
(%)
Ph
2PF6 – BAr f–
Ph
L
Time Conversion ee
(h)
(%)
(%)
O
MeO
O
OMe
NO 2
15
>99
88
10
94
90
4
>99
86
OMe
NO 2
22
98
94
7
98
97
4
>99
94
O
MeO
O
Ph
1
2
3
4
Kauffman, G. B. Coord. Chem. Rev. 1974, 12, 105-149.
Werner, A. Chem. Ber. 1911, 44, 1887-1898 and 1912, 45, 121-130.
Ganzmann, C.; Gladysz, J. A. Chem. Eur. J. 2008, 14, 5397-5400.
Ghosh, S. K.; Ojeda, A. S.; Guerrero-Leal, J.; Bhuvanesh, N.; Gladysz, J. A. Inorg. Chem. 2013,
52, 9369-9378.
5 Thomas, C.; Gladysz, J. A. ACS Catalysis 2014, 5, 1134-1138.
18
PL10
COMPLEXITY IN SIMPLICITY: THE PROTOTYPE REACTIONS OF
CARBENE ANALOGS
M.P. Egorov
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47,
Moscow, 119991, Russia
19
PL11
SELECTIVELY ALKYLATED AND ARYLATED N-HETEROAROMATICS
VIA ACCEPTORLESS DEHYDROGENATIVE CONDENSATION
(ADC) REACTIONS
R. Kempe
Lehrstuhl Anorganische Chemie II (Catalyst Design),University of Bayreuth, Bavaria, Germany
Dwindling reserves of crude oil and the resulting price increase of this and other fossil carbon
sources combined with environmental concerns have resulted in a call for the use of alternative,
preferably renewable, resources. Aside from fuel, ultimately a wide variety of chemical feedstocks
are derived from fossil sources. Renewable lignocellulosic materials are indigestible and therefore
not useful as food products and can be processed to give alcohols and polyols. These rather highly
oxidized hydrocarbons differ drastically in their chemical nature from the cracking products of
crude oil. Thus, there is a high demand for new reactions that utilize alcohols and convert them into
key chemicals. Recently, our group developed a sustainable catalytic pyrrole synthesis.[1]
Secondary alcohols and amino alcohols are deoxygenated and linked selectively via the formation
of C–N and C–C bonds. Two equivalents of hydrogen gas and two equivalents of water are
eliminated in the course of the reaction (Acceptorless Dehydrogenative Condensation, ADC).
Alcohols based entirely on renewable resources can be used as starting materials. The catalytic
synthesis protocol tolerates a large variety of functional groups, which includes olefins, chlorides,
bromides, organometallic moieties, amines and hydroxyl groups. Furthermore, we have developed a
catalyst that operates efficiently under mild conditions. This methodology could also be used to
synthesize selectively functionalized pyridines from alcohols.[2] In the talk, the development of
alcohol re-functionalization reactions and the design of catalyst systems that mediate these reactions
are discussed.
[1] S. Michlik, R. Kempe, Nature Chem. 2013, 5, 140.
[2] S. Michlik, R. Kempe, Angew. Chem. Int. Ed., 2013, 52, 6450.
20
PL12
THE CATALYST TODAY: BIG BANG AND LIFE AFTER
I.P. Beletskaya
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
Nanocatalysis and catalysis by Lewis and Broensted acids will be considered in the lecture.
21
Invited Lectures
22
23
IL1
CYCLIZATIONS OF ALKYNES: FROM STEREOELECTRONICS TO
CASCADE TRANSFORMATIONS
I.V. Alabugin
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Fl
One of the simplest organic functional groups, the alkyne moiety, is also one a useful starting point
for the design of cascade transformations which proceed through the formation of multiple C-C, CH, C-N and C-O bonds. [1] In this talk, I will illustrate how the revised stereoelectronic rules for
alkyne cyclizations [2] can be used for the bottom-up preparation of carbon nanostructures for
molecular electronics (i.e., graphene nanoribbons). In our approach, alkyne chains of varying sizes,
shapes and functionalities, are built in a modular fashion and “zipped” up into graphene
substructures via controlled cascades of all-exo or all-endo cyclizations. [3]
Even in the presence of multiple functionalities, alkyne cascades can be made chemoselective via
kinetic self-sorting of the pool of equilibrating radicals. [4] Further synthetic opportunities are
presented by fusion of cyclization cascades with self-terminating fragmentations that allow use of
alkenes as synthetic equivalents of alkynes. [5]
[1] Alabugin, I. V.; Gold, B. J. Org. Chem., 2013, 78, 7777.
[2] Alabugin, I. V.; Gilmore, K.; Manoharan, M. J. Am. Chem. Soc. 2011, 133, 12608. Alabugin, I.
V.; Gilmore, K. Chem. Commun., 2013, 49, 11246.
[3] Byers, P. M.; Rashid, J. I.; Mohamed, R. K.; Alabugin, I. V. Org. Lett., 2012, 14, 6032. Byers,
P.; J. Am. Chem. Soc. 2012, 134, 9609.
[4] Mondal, S.; Mohamed, R. K.; Manoharan, M.; Phan, H.; Alabugin, I. V. Org. Lett., 2013, 15,
5650.
[5] Mondal, S.; Gold, B.; Mohamed, R. K.; Alabugin, I. V. Chemistry – Eur. Journal, 2014, in
print.
24
IL2
ARTIFICIAL PHOTOSYNTHESIS USING TRANSITION METAL
COMPLEXES
O. Ishitani
Department of Chemistry, Tokyo Institute of Technology, Japan
Both the problems of the global warming and shortage of the fossil fuels have brought about great
interest in photochemical utilization of CO2 with solar energy. Efficient photocatalysts for CO2
reduction must be necessary for development of such an important technology.
We have developed novel types of photocatalytic systems using metal complexes and/or
semiconductors as a photocatalyst.1 In this presentation, I will focus on the architecture of two
types of the photocatalysts using transition metal complexes:
(1) A mixed photocatalytic system including a ring-shaped Re(I) multinuclear complex as a
photosensitizer2
(2) Ru(II)-Re(I) and Ru(II)-Re(I) supramolecular photocatalysts.3
The efficiency of the former photocatalytic system has been highest in the reported CO2-reduction
photocatalysts ( = 82%), and the latter photocatalysts have been most robust (TON > 3000).
References
1. (a) Yui, T.; Tamaki, Y.; Sekizawa, K.; Ishitani, O., Photocatalytic reduction of CO2: from
molecules to semiconductors. Top. Curr. Chem. 2011, 303, 151-84; (b) Sekizawa, K; Maeda, K.;
Domen, K.; Koike, K.; Ishitani, O. J. Am. Chem. Soc. 2013, 135, 4596.
2. Morimoto, T; Nishiura, C.; Tanaka, M.; Rohacova, J.; Nakagawa, Y.; Funada, Y.; Koike, K.;
Yamamoto, Y.; Shishido, S.; Kojima, T.; Saeki, T.; Ozeki, T.; Ishitani, O. J. Am. Chem. Soc.
2013, 135, 13266.
3. (a) Gholamkhass, B.; Mametsuka, H.; Koike, K.; Tanabe, T.; Furue, M.; Ishitani, O. Inorg.
Chem. 2005, 44, 2326; (b) Sato, S.; Koike, K.; Inoue, H.; Ishitani, O. Photochem. Photobiol. Sci.
2007, 6, 454; (c) Koike, K.; Naito, S.; Sato, S.; Tamaki, Y.; Ishitani, O. J Photochem. Photobiol.
A: Chem. 2009, 207, 109; (d) Tamaki, Y.; Watanabe, K.; Koike, K.; Inoue, H.; Morimoto, T.;
Ishitani, O. Faraday Discuss. 2012, 155, 115; (e) Tamaki, Y.; Morimoto, T.; Koike, K.; Ishitani,
O. Proc. Natl. Acad. Sci. USA 2012, 109, 15673. (f) Tamaki, Y.; Koike, K.; Morimoto, T.;
Ishitani, O. J. Cat. 2013, 135, 22; (g) Tamaki, Y.; Koike, K.; Morimoto, T.; Yamazaki, Y.;
Ishitani, O. Inorg. Chem. 2013, 52, 11902.
25
IL3
A PARADIGM FOR THE PRACTICAL AND ECONOMICAL FORMATION
OF CARBON—CARBON AND CARBON—HETEROATOM BONDS.
ORGANOCATALYTIC REDOX COUPLED, TRANSITION METAL
CATALYZED DEHYDRATIVE BOND CONSTRUCTIONS
L.S. Liebeskind, M.G. Lindale
Emory University, Department of Chemistry, Atlanta, Georgia USA
The current world-wide focus on C-H functionalization is driven, in part, by the conceptual promise
of atom-efficient, sustainable syntheses from readily available feedstocks. Of equal conceptual
value is the dehydrative formation of C—C, C—N, and C—O bonds from common bioavailable
hydroxylic reactants like carboxylic acids, alcohols, and phenols. Given the sustainable generation
of hydroxylic feedstocks, dehydrative bond formations can impact all levels of synthesis
(commodities, fine chemicals, biologicals), if they are efficient, economical, practical, and substrate
general. And, they are uniquely poised to contribute to the search for the sustainable conversion of
biomass to biofuels. This lecture describes a paradigm for the conversion of hydroxylic reactants to
value-added C—C, C—N, and C—O products based on a practical, organocatalytic redox-coupled,
transition metal catalyzed dehydrative bond forming process.
26
IL4
CHEMICAL SYNTHESIS USING AMPHOTERIC MOLECULES
A.K. Yudin
University of Toronto
Over the past seven years, my lab has been exploring the use of amphoteric molecules in chemical
synthesis. What started as a curiosity-driven project, has turned into a sustained exploration of a
virtually untouched segment of chemistry characterized by molecules with unusual combinations of
functional groups. The multifunctional nature arising from forced orthogonality enables amphoteric
molecules to participate in reactions of high atom- and step- economy, thereby enabling efficient
syntheses characterized by minimal reliance on protecting groups.
In this lecture, I will illuminate several classes of reagents developed in our lab. I will discuss the
discovery of bench-stable aldehydes equipped with a C-B bond at the alpha position. These
intriguing molecules have enabled the synthesis of a rich palette of other reagents that contain
carbon-boron bonds at strategic positions. With the growing repertoire of boron-containing
amphoteric molecules, we are in a good position to explore ideas that range from reaction discovery
to the synthesis of boron-based biologically active compounds.
I will also present the evolution of peptide macrocyclization technology driven by amphoteric
aziridine aldehydes. As part of this study, we are attempting to understand the conformational
preferences of peptide macrocycles. As a result, we are moving closer to our ultimate goal of
rationalizing the behavior of a wide range of substrate classes in our cyclization reactions, as well as
understanding cellular activity of macrocycles. I will conclude my talk with a discussion of our
integrative macrocyclization approaches and will present recent results of our protein crystallization
efforts.
27
IL5
EMERGENT FUNCTION FROM COMPLEX ADAPTIVE CATALYSTS
V.V. Fokin
The Scripps Research Institute, Department of Chemistry, La Jolla, California, USA and Moscow
Institute of Physics and Technology, Dolgoprudny, Russia
Exploiting the versatility of catalytic processes requires rigorous interrogation of the constantly
changing environment of the catalyst. Detailed understanding of critical events affecting a catalyst,
such as activation and deactivation, unproductive off-cycle pathways, and changes in the nature of
dominant species are of critical importance. The seemingly formidable challenge of controlling the
reactivity of complex catalytic systems that involve dynamic and rapidly equilibrating mixtures of
intermediates may, in fact, be their advantage: well-defined (i.e. non-adaptable) catalysts are often
inefficient when compatibility with many functional groups and conditions is the goal.
Examples of investigation of such catalytic reactions will be illustrated by case studies of transition
metal-catalyzed transformations of alkynes. Alkynes are among the most energetic hydrocarbons,
and transition metals enable selective and controlled manipulation of the triple bond, revealing their
unique reactivity: transformations of alkynes into heterocycles and into a variety of molecules with
new carbon–heteroatom bonds. These seemingly simple transformations involve an impressive
variety of intermediates yet proceed with high selectivity and efficiency, maintaining their reactivity
in most complex environments, such as the biological milieu of living organisms.
28
IL6
RAPID PHOTOASSISTED ACCESS TO sp3-RICH POLYHETEROCYCLIC
SCAFFOLDS
O.A. Mukhina, N.N.B. Kumar, W.C. Cronk, W.J. Umstead, A.G. Kutateladze
Department of Chemistry and Biochemistry, University of Denver, USA
Photochemical reactions hold unparalleled promise for building prohibitively strained carbo‐ and
heterocyclic scaffolds, which offer expeditious access to difficult synthetic targets not accessible via
ground state chemistry. Yet, photochemistry is underutilized by the synthetic community, which is
especially true for Diversity Oriented Synthesis (DOS). In this context we have been developing a
new photoassisted synthetic methodology which will enhance synthetic chemistry toolbox and will
be compatible with DOS.1 This new photoassisted synthetic methodology allows for rapid access
to topologically diverse polycyclic scaffolds decorated by various functional groups and
carbo/heterocyclic pendants rigidly or semi-rigidly held in a unique spatial configuration by these
novel core frameworks. Access to such topologically diverse scaffolds is realized via key
photochemical steps and their combination with ground state reactions, most prominently via the
recently discovered intramolecular cycloaddition reactions of azaxylylenes and quinomethanes
photogenerated via excited state intramolecular proton transfer. Details of an experimental and
theoretical mechanistic study to gain deeper understanding of underlying processes in the excited
states will also be discussed.
A typical example of rapid growth of complexity in a photoassisted synthesis of enantiopure
conformationally locked ribofuranosylamines spiro-linked to oxazolidino-diketopiperazines via a
straightforward “assembly” of a threonine-based photoprecursor, photochemical transformation,
and a simple post-photochemical modification, is shown below.
[1] (a) Mukhina, O.A.; Kumar, N.N.B.; Arisco, T.M.; Valiulin, R.A.; Metzel, G.A.; Kutateladze,
A.G. Angew. Chem. Int. Ed., 2011, 50, 9423-9428. (b) Nandurkar, N.S.; Kumar, N.N.B.;
Mukhina, O.A.; Kutateladze, A.G. ACS Combinatorial Sci., 2013, 15, 73-76. (c) Kumar,
N.N.B.; Mukhina, O.A.; Kutateladze, A.G. J. Am. Chem. Soc., 2013, 135, 9608-9611. (d)
Cronk, W.C.; Mukhina, O.A.; Kutateladze, A.G. J. Org. Chem., 2014, 79,1235-1246.
29
IL7
TRANSITION METAL CLUSTERS: UNAVOIDABLE CONTAMINANTS OR
IMPORTANT PLAYERS IN SOLUTION?
V.P. Ananikov
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47,
Moscow, 119991, Russia; Department of Chemistry, Saint Petersburg State University, Stary
Petergof, 198504, Russia
Application of transition metal catalysis in organic synthesis is an area of outstanding progress with
prominent achievements in carbon-carbon cross-coupling, carbon-heteroatom bond formation, and
atom-economic construction of organic molecules.
Mechanistic studies have revealed two different frameworks for catalytic processes in solution
depending on the nature of selected system and on the type of catalyst precursor used: single type
metal species catalysis or multiple metal species catalysis [1]. The first type of systems is widely
utilized and it is based on well-defined metal complex with strongly bound ligands. The catalyst
precursor undergoes only partial or minor chemical modifications prior entering the catalytic cycle.
In this model, the formation of other metal derivatives is not facilitated and the active core of the
catalyst is preserved throughout the catalytic cycle.
The second model can be considered as multiple metal species catalysis (in some cases - “cocktail”
of catalysts) and involves a range of simultaneously present and dynamically interchangeable metalcontaining species, such as metal complexes, clusters and nanoparticles [2]. Such mechanistic
picture may be expected when in situ generated catalysts are employed or upon usage of
nanoparticles as catalysts precursors.
It is of much interest to reveal the role of metal clusters in these catalytic systems. Formation of
clusters was detected in many cases, although their role remains unclear. In some cases the presence
of clusters was related to decomposition of the active form, while in the other cases the formation of
dinuclear and polynuclear species is an important stage of catalyst evolution in solution.
We have investigated soluble metal complexes and nanoparticles of Pd, Ni, Pt and Au for
development of efficient catalytic systems for selective carbon-heteroatom and carbon-carbon bond
formation in solution [3-5]. Homogeneous transition-metal-catalyzed reactions and heterogeneous
nanoparticle-catalyzed reactions were considered, with a focus on metal species interconversions
and nanoparticle contamination of homogeneous catalytic systems.
References
[1] Kashin A.S., Ananikov V. P., J. Org. Chem., 2013, 78, 11117 (doi: 10.1021/jo402038p).
[2] Ananikov V. P., Beletskaya I. P., Organometallics, 2012, 31, 1595 (doi: 10.1021/om201120n).
[3] Zalesskiy S. S., Sedykh A. E., Kashin A. S., Ananikov V. P., J. Am. Chem. Soc., 2013, 135,
3550 (doi: 10.1021/ja311258e).
[4] Ananikov V. P., Orlov N. V., Zalesskiy S. S., Beletskaya I. P., Khrustalev V. N., Morokuma
K., Musaev D. G., J. Am. Chem. Soc., 2012, 134, 6637 (doi: 10.1021/ja210596w).
[5] Kashin A. S., Ananikov V. P., Top. Catal., 2013, 56, 1246 (doi: 10.1007/s11244-013-0091-5).
30
IL8
SIMPLE COPPER CATALYSTS FOR C-C, C-N AND C-O BONDS
FORMATION
F. Monnier
Institut Charles Gerhardt (UMR 5253) ENSCM, FRANCE
Since its renaissance in 2001, [1] the copper cross-coupling of nucleophiles with aryl halides has
been increasingly studied. [2] In this account, we exposed our last contribution for the formation of
C-C, [3] C-N [4] and C-O [5] bonds catalyzed by a cheap and simple combination of copper salts
and -diketone ligands.
1. a) M. Taillefer, H.-J. Cristau, P. P. Cellier, J.-F.Spindler, Env. SAU2001-1009 and SAU200101044; patents Fr2833947-WO0353225 (Pr. Nb. Fr 2001 16547); M. Taillefer, H.-J. Cristau, P.
P. Cellier, J.-F. Spindler, A. Ouali, Fr2840303-WO03101966 (Pr. Nb. Fr 2002 06717); b) S. L.
Buchwald, A. Klapars, J. C. Antilla, G. E. Job, M. Wolter, F. Y. Kwong, G. Nordmann, E. J.
Hennessy,WO02/085838 (priority number US0286268, 2001)
2. For a review, see: F. Monnier, M. Taillefer Angew. Chem., Int. Ed. 2009, 48, 6954-697
3. a) G. Danoun, A. Tlili, F. Monnier, M. Taillefer Angew. Chem. Int. Ed., 2012, 51, 12815. b)
M.Taillefer, F. Monnier, A. Tlili, G. Danoun. PCT Int. Appl. (2013), WO 2013 EP61697
20130606; FR20120055275 20120606.
4. a) A. Tlili, F. Monnier, M. Taillefer Chem. Commun., 2012, 48, 6408-6410. b) E. Racine, F.
Monnier, J.-P. Vors, M. Taillefer Chem. Commun., 2013, 49, 7412. c) E. Racine, F. Monnier, J.P. Vors, M. Taillefer Org. Lett. 2011, 13, 2818.
5. a) A. Tlili, N. Xia, F. Monnier, M. Taillefer Angew. Chem., Int. Ed., 2009, 48, 8725-8728.
31
IL9
INTERACTIONS IN IONIC LIQUIDS PROBED BY NMR SPECTROSCOPY:
DISTANCES, CONFORMATIONS, AND MORE
R. Giernoth, A. Broehl, Y. Lingscheid
University of Cologne, Department of Chemistry, Koeln, Germany
One often-mentioned aspect of ionic liquids (ILs) is that they are “designer solvents“ whose
properties can be designed for any particular need [1]. Obviously, it is impossible to choose a
different property for a given IL but only a different IL entirely. To be able to sensibly do so, it is
necessary to know about the supramolecular structures and the governing interactions in the ionic
liquid phase.
NMR spectroscopy and the nuclear overhauser effect
spectroscopy (NOE) in particular is the method of choice
for the investigation of ion pair interactions [2]. The
NOE arises due to inter- and intramolecular cross
relaxation.
To be able to precisely measure interactions in solution,
an internal distance standard is needed. We have
synthesized a monofluorinated ionic liquid which was subsequently employed in NOE-based NMR
investigations for the determination of distances and interactions in the ionic liquid phase.
In a different project, we are studying the influence of
different ionic liquids on peptide conformations, much
in accord with the well-known Hofmeister series of ions
[3]. With the help of a model system we are going to
demonstrate that the choice of ions has a strong effect on
the tertiary structure of different peptides in solution,
and how these effects can be used for new non-native
peptide chemistry.
References
[1] for reviews see: J.P. Hallett, T. Welton, Chem. Rev., 2011, 111, 3508-3576; E. J. Maginn, J.
Phys. Condens. Matter, 2009, 21, 1–17.
[2] P. S. Pregosin, Pure Appl. Chem., 2009, 81(4), 615–633; Y. Lingscheid, S. Arenz, R. Giernoth,
ChemPhysChem 2012, 13, 261–266.
[3] F. Hofmeister, Arch. Exp. Pathol. Pharmakol., 1888, 64, 247.
32
IL10
APPLICATION OF α-CF3-SUBSTITUTED DIAZOCOMPOUNDS IN
ORGANIC SYNTHESIS AND CATALYSIS
S.N. Osipov, D.V. Vorobyeva, I.E. Tsishchuk
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow
An efficient pathway to multifunctional CF3-containing aromatic, heteroaromatic and heterocyclic
compounds, including cyclic amino carboxylic and amino phosphonic acid derivatives have been
developed. The method is based on in situ generation of highly electrophilic CF3-carbene species
from the corresponding α-diazo carboxylates or phosphonates under Cu- or Rh-catalysis and their
reactions with appropriate nucleophilic partners.1-4
The further applications of the reaction products in metal-catalysed transformations of different
types, e.g. such as ring closing diene and ene-yne metathesis, intramolecular Pauson-Khand
reaction as well as [2+2]-cycloaddition, open an access to new families of fluorinated molecules.
References:
1. D.V. Vorobyeva, A.K. Mailyan, A.S. Peregudov, N.M. Karimova, T.P. Vasilyeva, I.S.
Bushmarinov, C. Bruneau, P.H. Dixneuf, S.N. Osipov, Tetrahedron, 2011, 67, 3524.
2. A.K. Mailyan, I.M. Krylov, C. Bruneau, P.H. Dixneuf, S.N. Osipov, Synlett, 2011, 2321.
3. A.K. Mailyan, I.M. Krylov, C. Bruneau, P.H. Dixneuf, S.N. Osipov, Eur. J. Org. Chem.,
2013, 5353.
4. I.E. Tsishchuk, D.V. Vorobyeva, A.S. Peregudov, S.N. Osipov, Eur. J. Org. Chem. 2014,
2480.
33
IL11
NEW ADVANCES IN ORGANOMETALLIC AND PHOSPHORUS
ELECTROCHEMISTRY
D.G. Yakhvarov, O.G. Sinyashin
A.E.Arbuzov Institute of Organic and Physical Chemistry, Laboratory of Organometallic and
Coordination Compounds, Kazan, Russian Federation
The development of modern chemical science and creation of new industrially applicable
technologies are focused on application of effective and ecologically safe methods for the
preparation of important and useful chemical compounds and materials. The combination of
transition-metal catalysis and organic electrosynthesis has attracted increasing attention due to the
high selectivity and efficiency of this approach in the synthetic preparation of various compounds
bearing carbon-carbon and carbon-element bonds. The mild conditions, single-stage process, cyclic
regeneration of the catalyst, and convenient and relatively inexpensive form of the energy used are
the main advantages of electrochemical methods. Application of electrochemical processes to largescale production (macroscale synthesis) has led to significant development of the chemical
technologies of the 21st century, due to easy access to highly reactive intermediates and tuning of
the reactivity of the substrate used during the synthetic process by simple adjustment of the
electrode potential.
The elaborated in our research group electrochemical methods have been successfully applied for
generation of organometallic sigma-complexes,1 which are important intermediates of different
carbon-carbon and carbon-element coupling processes, selective preparation of organophosphorus
compounds from white phosphorus,2 activation of inert oligophosphorus moieties formed in the
coordination sphere of transition metal complexes,3 selective cleavage of the tungsten-phosphorus
bond resulting in valuable metal-free phosphorus heterocycles obtained via phosphinidene
intermediates.4
Herein, we present recent advances in synthetic application of the electrochemical techniques for
preparation and activation of organonickel complexes1 and generation of new, previously known as
unstable, phosphorus intermediates,5 which can be applied for preparation of practically useful
organophosphorus compounds, transition metal catalysts and magnetically active materials.6
Acknowledgements: Financial support from the Russian Scientific Fund (project 14-13-01122) and
Russian Foundation for Basic Research (project 09-03-00933-a) is gratefully acknowledged.
References:
[1] D.G.Yakhvarov, A.F.Khusnuriyalova, O.G.Sinyashin. Organometallics, 2014, in press.
[2] D.G.Yakhvarov, E.V.Gorbachuk, O.G.Sinyashin. Eur. J.Inorg.Chem., 2013, 4709.
[3] D.Yakhvarov, P.Barbaro, L.Gonsalvi, S.Mañas, S.Midollini, A.Orlandini, M.Peruzzini,
O.Sinyashin, F.Zanobini. Angew. Chem. Int. Ed., 2006, 45, 4182.
[4] D.G.Yakhvarov, Yu.H.Budnikova, N.H.Tran Huy, L.Ricard, F.Mathey. Organometallics,
2004, 23, 1961.
[5] D.Yakhvarov, M.Caporali, L.Gonsalvi, Sh.Latypov, V.Mirabello, I.Rizvanov, O.Sinyashin,
P.Stoppioni, M.Peruzzini. Angew. Chem.Int.Ed., 2011, 50, 5370.
[6] D.Yakhvarov, E.Trofimova, O.Sinyashin, O.Kataeva, P.Lönnecke, E.Hey-Hawkins, A.Petr,
Yu.Krupskaya, V.Kataev, R.Klingeler, B.Büchner. Inorg. Chem., 2011, 50, 4553.
34
IL12
TRIFLUOROMETHYLATION BY SUNLIGHT-PROMOTED
PHOTOREDOX CATALYSIS
T. Koike, M. Akita
Tokyo Institute of Technology, Chemical Resources Laboratory, Yokohama, Japan
Photoredox catalysis 1 mediated by photo-sensitizers (e.g. [Ru(bipy)3]2+ and relevant Ir complexes)
has attracted increasing attention as practical, green synthetic chemical processes, because they are
visible light-promoted, redox-neutral reactions.
We have demonstrated that photoredox catalysis is a powerful synthetic tool, in particular, for
trifluoromethylation of olefinic substrates, which is the topic of the presentation.2,3 In all cases,
electron transfer from the photoexcited metal species to an electrophilic CF3-reagent generates the
key CF3 radical intermediate together with the cationic species of the catalyst. Subsequent
addition of the CF3 radical to the olefinic substrate followed by oxidation of the resultant carbon
radical intermediate by the cationic metal species gives the carbocationic intermediate, which is
trapped by nucleophiles or deprotonated to furnish the coupling products. The sequential redox
processes make the system redox-neutral. It is remarkable that the reactions are promoted not only
by artificial light sources (e.g. Xe lamp and blue LED lamps) but also by sunlight.
References: 1) C. K. Prier, D. A. Rankic, and D. W. C. MacMillan, Chem. Rev., 113, 5322 (2013).
2) T. Koike and M. Akita, (a) Synlett., 24, 2492 (2013); (b) Topics in Cat., 259, in press (2014)
(DOI: 10.1007/s11244-014-0259-7). 3) Y. Yasu, T. Koike, M. Akita et al., (a) Angew. Chem., Int.
Ed., 51, 9567 (2012); (b) Chem. Commun., 49, 2037 (2013); (c) Org. Lett., 15, 2136 (2013); (d)
Org. Lett., 16, in press (2014) (DOI: 10.1021/ol403500y); (e) Beilstein J. Org. Chem., submitted;
(f) to be submitted; see also (g) Chem. Commun., 48, 5355 (2012); (h) ibid., 49, 7249 (2013).
35
IL13
CYCLIC HYPERVALENT IODINE REAGENTS: A TREASURE OF
REACTIVITY FOR CATALYSIS AND SYNTHESIS
J. Waser
Ecole Polytechnique Federale de Lausanne, ISIC SB LCSO, Lausanne, Switzerland
The non-classical four electrons three centers bonds of hypervalent iodine are weaker than normal
classical bonds. This confers an exceptional reactivity to these compounds as oxidants or atomtransfer reagents. Cyclic hypervalent iodine reagents are especially interesting, as they combine
enhanced stability with unique opportunities for reactivity modulation. In particular, our group has
been interested in the development of alkynylation methods using cyclic EthynylBenziodoXolone
(EBX) hypervalent iodine reagents.1 Interesting recent results of our research in the area includes
the first example of gold-catalyzed domino cyclization-alkynylation2 and a highly efficient and
practical alkynylation method for thiols.3 Herein, we will present our most recent work in the area
of electrophilic alkynylation, as well as the extension of the use of cyclic hypervalent iodine
reagents to other functionalization reactions.
References:
1. J.P Brand, J. Waser, Chem. Soc. Rev. 2012, 41, 4165-4179.
2. Y. Li, J. P. Brand, J. Waser, Angew. Chem., Int. Ed. 2013, 52, 6743-6747.
3. R. Frei, J. Waser, J. Am. Chem. Soc. 2013, 135, 9620-9623.
36
IL14
THEORY AND COMPUTATION PROVIDE INSIGHTS AND DISCOVERY
ON CHEMICAL REACTIONS OF COMPLEX MOLECULAR SYSTEMS
K. Morokuma1,2
1 - Fukui Institute for Fundamental Chemistry; Kyoto University, Kyoto, Japan
2 - Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory
University, Atlanta, GA, USA
The chemical reaction that creates, destroys, reorganizes chemical bonds to produce new
compounds is the most important subject of chemistry. Theoretical/computational studies have
come a long way and are now playing the central role in providing insights in understanding the
mechanism and dynamics of chemical reactions as well as in discovery of new reaction mechanisms
and reaction systems. The theory can study not only the reaction of the ground state of molecules in
gas phase but also reactions of excited electronic states as well complicated reactions of complex
molecular systems. The information theoretical/computational studies can provide is often
complementary to the information experimental studies provide, and research on chemical reactions
is becoming impossible without strong collaboration between theorists and experimentalists.
In the present talk, I will discuss some of our recent studies of chemical reactions. We have
developed the Global Reaction Route Mapping (GRRM) strategy for automatic exploration of
reaction pathways of complex molecular systems. The ADDF (anharmonic downward distortion
following) and the AFIR (artificial force induced reaction) methods in the GRRM strategy have
been used for determination of not only energy minima and saddle points on the potential energy
hypersurfaces but also minima and saddle points on the conical intersection and crossing seam
hypersurfaces. I will discuss the GRRM strategy and applications to several reaction systems,
including photodissociation reactions, catalytic reactions and enzymatic reactions.
37
IL15
COMPUTATIONAL INSIGHTS INTO C-H FUNCTIONALIZATION
JUNGLE
D. Musaev
Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia, U.S.A
I will present our integrated and
C-H FUNCTIONALIZATION
SELECTIVE
collaborative approaches to the RSH/RSeH + C C Pd(II)- PRECATALYST DIRECT Ar-Ar COUPLING
Transition metal catalyzed C-H bond
F
ZR
ZR
ZR
Cs
Cs
functionalization. I will elaborate our
Pd
Pd
Pd
O H
O
Ph
H
O i-Pr
efforts on understanding the transition RZ ZR ZR
I
Active
O
ZR
metal catalyzed C-H bond alkylation
N
Pd
Pd H
ZR
H
N
Pd
and amination reactions, and analyze
Pd
Ar
Ph
PG
Inactive
PR3
the factors controlling the reactivity of RZ ZR Pd ZR ZR
"Cs2-I-F" assisted
Ligand accelerated
these reactions and make intriguing Pd-cluster effect
Base (Cs)-effect
Protecting Group effect
predictions. I will discuss our latest
results [1] on the mono-protected amino acid ligands (MPAA) promoted Pd(II)-catalyzed
enantioselective C–H activation reactions. The presented computation allowed us to gain insights
into the mechanisms, nature of active species, a ligand coordination mode to the Pd(II) and
transition state structure of the C–H activation step. Our findings were supported by experiments.
[1] D. G. Musaev, T. M. Figg, and A. L. Kaledin, Chem. Soc. Rev., DOI: 10.1039/C3CS60447K,
(2014).
38
IL16
A NOVEL TRIFLUOROMETHANESULFONYL HYPERVALENT
IODONIUM YLIDE FOR TRIFLUOROMETHYLTHIOLATION
N. Shibata
Nagoya Institute of Technology, Department of Nanopharmaceutical Sciences, Nagoya, Japan
In the last few decades, numerous methods for the introduction of a trifluoromethylthio group into
organic compounds have been developed. The main strategies are indirect methods, including
halogen-fluorine exchange and trifluoromethylation of sulfur-containing compounds, such as
disulfides, thiols and thiolates. Obviously, the most attractive and ideal route to constitute the CF3S
moiety is the direct introduction of this functional group. However, in this approach, some
limitations are usually encountered, including the use of gaseous and highly toxic reagents, such as
CF3SCl, or unstable reagents, and the modest scope of substrates. Although several transition
metal-mediated or catalyzed trifluoromethylthiolation methods have been developed, the substrates
are mostly limited to aromatic compounds. Recently, Billard and co-workers reported that
trifluoromethanesulfanylamides were effective for trifluoromethylthiolation of alkenes, alkynes,
indoles and organometallic species. More recently, Lu and Shen also developed a novel hypervalent
iodine reagent for the trifuoromethylthiolation of aryl and vinyl boronic derivatives, alkynes and βketoesters. Even though these direct trifluoromethylthiolation reagents are shelf-stable, a more
critical issue is the fact that these CF3S regents should be prepared in advance by
trifluoromethylthiolations or related trifluoromethylations! Due to these limitations and negative
aspects, it is thus still necessary to develop an efficient and easily available reagent to introduce the
CF3S moiety directly. In contrast to the CF3S unit, a trifluoromethanesulfonyl (CF3SO2) unit is
stable and often found in commonly used organic reagents such as CF3SO2Cl, CF3SO2Na, CF3SO2H
and (CF3SO2)2. In this context, we came up with a novel idea of using ubiquitous CF3SO2
compounds as reagents for introducing the CF3S unit under reductive conditions. As a part of our
recent work on the chemistry of trifluoromethanesulfonyl compounds (triflones), we herein disclose
a novel trifluoromethanesulfonyl hypervalent iodonium ylide as a shelf-stable reagent for
electrophilic-type trifluoromethylthiolation. A wide variety of nucleophiles are nicely converted
into the corresponding trifluoromethylsulfanyl products by this reagent.
Reference: Y.-D. Yang, A. Azuma, E. Tokunaga, M. Yamasaki, M. Shiro, N. Shibata, J. Am.
Chem. Soc., 135, 8782 (2013)
39
IL17
CATALYSIS-ASSISTED SIGNAL ENHANCEMENT IN NUCLEAR
MAGNETIC RESONANCE
I.V. Koptyug
International Tomography Center, SB RAS, Novosibirsk, Russia
When parahydrogen (nuclear spin isomer of H2) is used in catalytic hydrogenations instead of
normal H2, the NMR signals of reaction products and intermediates can be enhanced by 3-4 orders
of magnitude and more owing to the phenomenon of parahydrogen-induced polarization (PHIP).
This possibility has been explored previously in the context of activation of H2 by transition metal
complexes and clusters in solution. It has been shown that PHIP can help to detect reaction products
and short-lived intermediates not detectable by conventional NMR. As most of the industrial
catalytic processes are heterogeneous, it would be desirable to employ PHIP in the NMR studies of
heterogeneous catalysts and catalytic reactions. The objective of our research is thus to extend the
scope of PHIP applications to the heterogeneously (HET) catalyzed hydrogenation reactions, and to
develop a hypersensitive NMR-based technique for the in situ and operando studies of
heterogeneous catalytic processes. In addition, HET-PHIP can be employed to produce catalyst-free
hyperpolarized liquids and gases for novel MRI applications including the advanced in vivo studies.
We demonstrate that, similar to their homogeneous counterparts, heterogenized transition metal
complexes are able to produce strong NMR signal enhancements when parahydrogen is used in the
hydrogenation reactions [1]. Our recent results show that various immobilized metal complexes are
can produce HET-PHIP both in liquid phase and in gas phase hydrogenations. In contrast, for
supported metal catalysts (e.g., Pt/Al2O3), dissociative hydrogen chemisorption and rapid migration
of H atoms on the metal surface were expected to make the required pairwise hydrogen addition to
a substrate molecule impossible. Nevertheless, we have shown that PHIP can be successfully
observed both in liquid-solid and in gas-solid heterogeneous hydrogenations catalyzed by supported
metal catalysts [1]. The NMR signal enhancement was found to be sensitive to the metal
nanoparticle size and shape, the nature of the metal and support, and the type of substrate used in
the reaction. Recently, HET-PHIP effects were also demonstrated for several metal oxides and bulk
unsupported metals used as hydrogenation catalysts [2]. The implications of these results for the
mechanisms of heterogeneous hydrogenation processes are discussed [1,3]. Further potential
extensions of the technique will be presented, including the use of metal-free catalysts for activating
parahydrogen [4], and the prospects of using nuclear spin isomers of molecules other than H2 to
further extend the range of reactions and processes that can be explored in detail using the PHIP
technique [5]. In addition to applying HET-PHIP to the mechanistic and kinetic studies of
heterogeneous hydrogenations, several MRI applications of HET-PHIP have been already
demonstrated, including MR imaging of a catalytic reaction in an operating model microreactor [6].
1. K.V. Kovtunov, V.V. Zhivonitko, I.V. Skovpin, D.A. Barskiy, I.V. Koptyug, Top. Curr. Chem., 338, 123
(2013).
2. K.V. Kovtunov, D.A. Barskiy, O.G. Salnikov, A.K. Khudorozhkov, V.I. Bukhtiyarov, I.P. Prosvirin, I.V.
Koptyug, Chem. Commun., 50, 875 (2014)
3. O.G. Salnikov, K.V. Kovtunov, D.A. Barskiy, A.K. Khudorozhkov, E.A. Inozemtseva, I.P. Prosvirin, V.I.
Bukhtiyarov, I.V. Koptyug, ACS Catal., 4, 2022 (2014).
4. V.V. Zhivonitko, V.-V. Telkki, K. Chernichenko, T.J. Repo, M. Leskela, V. Sumerin, I.V. Koptyug, J.
Amer. Chem. Soc., 136, 598 (2014).
5. V.V. Zhivonitko, K.V. Kovtunov, P.L. Chapovsky, I.V. Koptyug, Angew. Chem. Int. Ed., 52, 13251
(2013).
6. V.V. Zhivonitko, V.-V. Telkki, I.V. Koptyug, Angew. Chem. Int. Ed., 51, 8054 (2012).
40
IL18
-BOND ACTIVATION REACTION BY TRANSITION METAL AND MAINGROUP ELEMENT COMPOUNDS AND CATALYTIC REACTION
INCLUDING IT
S. Sakaki
Fukui Institute for Fundamental Chemistry, Kyoto University, Takano, Sakyo-ku, Kyoto 606-8103,
Japan
The -bond activation by transition metal complexes attracts a lot of interests in theoretical and
organometallic chemistries, because it is crucial in many catalytic reactions by transition metal
complexes. In our understanding, -bond activation is classified to two categories; the concerted
oxidative addition to M (metal), the stepwise oxidative addition via nucleophilic attack, the
oxidative addition to M-L (L = neutral ligand), and the heterolytic activation by M-X (X = anionic
ligand). activation by metal center only and that by the metal-ligand moiety.1,2
MLn + R1-R2  cis-MLn(R1)(R2)
(1)
1
1
MLn + R1-X  [MLn(R )] --(X)  trans-MX(R )Ln
(2)
MLLn + R1-R2  MLn(R1)(L-R2)
(3)
1
2
MXLn + R1-R2  MLn(R ) + R -X
(4)
We theoretically investigated these reactions and elucidated the characteristic electronic processes
and clear understanding.2 We also theoretically investigated catalytic reactions including -bond
activation. In this talk, we wish to present our recent theoretical studies of carboxylation of
phenylchloride catalysed by a nickel(0) complex, hydrosilylation of carbon dioxide catalyzed by
germanium(II)- and zinc(II)-hydride compounds.3
In my talk, I wish to present comprehensive understanding of these -bond activation reactions and
the importance of -bond activation reaction in such catalytic reactions as CO2 conversion and
cross-coupling reactions.
References.
1. S. Sakaki, Y.-y. Ohnishi, H. Sato, Chem. Record., 10, 29 (2010). W. Guan, F. B. Saeed, S.
Sakaki, Inorg. Chem., in press.
2. N. Ochi, Y. Nakao, H. Sato, S. Sakaki, J. Am. Chem. Soc., 129, 8615 (2007). N. Ochi, Y. Nakao,
H. Sato, S. Sakaki, J. Phys Chem. A, 114, 659 (2010).
3. N. Takagi and S. Sakaki, J. Am. Chem. Soc., 135, 8955 (2013). M. Deschmukh, to be submitted.
41
IL19
NONPLANAR HETEROAROMATICS: SYNTHESIS AND SELF-ASSEMBLY
M. Stepien
Wydziaі Chemii, Uniwersytet Wrocіawski
Even though π-electron aromaticity is typically associated with planar structures, several classes of
distorted π-aromatics are known, including a variety of twisted, helical, bowl-shaped, or tubular
systems. Such distortions are of fundamental interest, because they provide a means of testing
different aspects of aromaticity theory, but they also may have practical consequences, as a
potential method of fine-tuning the electronic structure and self-assembly properties of aromatic
compounds.
In this contribution, two synthetic approaches to nonplanar heteroaromatics will be discussed. One
is based on oxidative coupling reactions of pyrrole-containing precursors, and is exemplified by our
recent syntheses of peripherally fused porphyrin derivatives1 (1 and 2) and bipyrroles.2 Compounds
1–2 are characterized by bathochromically shifted electronic absorptions and very high extinction
coefficients. Phenanthroporphyrins 1 and their complexes reveal substitution-dependent aggregation
in solution and form columnar mesophases in the condensed phase. The zinc(II) complex of
benzochrysenoporphyrin 2 was found to form a unique 3D-ordered mesophase containing discrete
multiporphyrin aggregates.
The other approach to nonplanar aromatics explored in our laboratory, which is suitable to the
synthesis of bowl- or belt-shaped structures, involves the so-called fold-in synthesis,3 performed on
appropriately designed macrocyclic precursors. The fold-in concept can be realized using different
reactivity types, including Ullmann-type reductive coupling, as in the recent synthesis of
chrysaorole (3),3,4 and Friedel–Crafts alkylation.5
(1) Myśliwiec, D.; Donnio, B.; Chmielewski, P. J.; Heinrich, B.; Stępień, M. J. Am. Chem. Soc.
2012, 134, 4822–4833.
(2) Gońka, E.; Myśliwiec, D.; Lis, T.; Chmielewski, P. J.; Stępień, M. J. Org. Chem. 2013, 78,
1260–1265.
(3) Stępień, M. Synlett 2013, 24, 1316–1321.
(4) Myśliwiec, D.; Stępień, M. Angew. Chem. Int. Ed. 2013, 52, 1713–1717.
(5) Kondratowicz, M.; Myśliwiec, D.; Lis, T.; Stępień, M. in preparation.
42
IL20
RHODIUM N-HETEROCYCLIC CARBENE COMPLEXES AS EFFICIENT
CATALYSTS FOR X-H ADDITIONS TO ALKYNES: THE QUEST FOR
SELECTIVITY
R. Castarlenas, A. Di Giuseppe, L. Rubio-Perez, L. Palacios, R. Azpiroz, V. Polo, J.J. PerezTorrente, L.A. Oro
ISQCH Universidad de Zaraaragoza-CSIC
The development of new catalytic systems for the synthesis of added-value products in a selective
manner and with high atom economy is nowadays an important task. In this context, our group has
recently prepared new rhodium complexes bearing an N-heterocyclic carbene (NHC) ligand that
have been disclosed to be very active and gem-selective for X-H additions across C-C triple
bonds.1-4 Experimental and theoretical (DFT) mechanistic studies indicate that the presence of a
bulky powerful electron-releasing NHC and the rational choice of the auxiliary ligands is essential
in order to control the selectivity towards the formation of Markonikov-type products.
1 A. Di Giuseppe, R. Castarlenas, J.J. Perez-Torrente, M. Crucianelli, V. Polo, R. Sancho, F.J.
Lahoz, L.A. Oro, J. Am. Chem. Soc. 2012, 134, 8171.
2 L. Palacios, M.J. Artigas, V. Polo, F.J. Lahoz, R. Castarlenas, J.J. Perez-Torrente, L.A. Oro, ACS
Catal. 2013, 3, 2910.
3 L. Rubio-Pérez, R. Azpíroz, A. Di Giuseppe, V. Polo, R. Castarlenas, J.J. Perez-Torrente, L.A.
Oro, Chem. Eur. J. 2013, 19, 15304.
4 R. Azpíroz, A. Di Giuseppe, R. Castarlenas, J.J. Perez-Torrente, L.A. Oro, Chem. Eur. J. 2013,
19, 3812.
43
IL21
CATALYTIC OLEFINATION REACTION – UNIVERSAL METHOD FOR
SYNTHESIS OF ALKENES
V.G. Nenajdenko
Moscow State University, Department of Chemistry, Leninskie Gory, Moscow 119992
Catalytic olefination reaction represents new approach to the preparation of double C=C bond. Nunsubstituted hydrazones can be converted into alkenes by treatment with polyhalogenated alkanes
in presence of a base and catalytic amounts of copper salts. The reaction has a wide synthetic scope
allowing to prepare both alkyl and aryl halogenoalkenes, including fluorinated ones and derivatives
with functional groups. Simple experimental procedure, which does not require using of
organometallic or toxic organophospourous compounds, affordable price and availability of starting
materials, high yields and stereoselectivity are distinct advantages of the reaction.
R1
1
R
R
R1
2
R
1
R1
CN
R2
Cl
R1
2
R
Br
Cl
Cl
2
R
F
CH2OH
R1
H
R2
Cl
R1
Cl
R1
COOR
H
2
O
R
Br
R1
H
2
R
R
Cl
R2
CONR2
R
Cl
F
2
R2
1
R
Br
2
R
1
R
CBrF2
1
R
F
Cl
R2
F
R2
I
1
F
2
CBrF2R2
R
1
R
1
1
F
2
Cl
R
Cl
R
F
CF3
R2
CClF2 R
CBrF2
R
44
O
O
IL22
HOW TO MAKE COMPLEX MOLECULES FROM SIMPLE STARTING
MATERIAL: THE PALLADIUM, A POWERFUL TOOL
J. Suffert
University of Strasbourg/CNRS
In addition to molecular complexity, the challenge of the chemist today is also the quest for
efficiency of the synthetic route and maximization of structural complexity. Our laboratory
investigations focus for several years on the study of an unprecedented cascade reaction involving a
rare 4-exo-dig cyclocarbopalladation followed by a terminated cross-coupling with an
organometallic reagent. A 6 - or 8 -electrocyclization can occur leading to new tricyclic structures.
The seminar will show that we can offer an easy access to complex polycyclic molecules resulting
from readily available simple starting materials. Eventually, it will be possible to propose the
elaboration of a large collection of unprecedented structurally novel molecules based on recent
promising results. Below are represented several complex structures that has been prepared through
the powerful 4-exo-dig cyclocarbopalladation. Many other extension of this method have not been
so far explored and can afford a multitude of new and original scaffolds.
45
IL23
SYNTHESIS OF TIN AND LEAD ANALOGS OF CYCLOPENTADIENYL
ANION AND THEIR APPLICATION TO TRANSITION-METAL
COMPLEXES
M. Saito
Department of Chemistry, Graduate School of Science and Engineering, Saitama University,
Shimo-okubo, Sakura-ku, Saitama-city, Saitama, 338-8570, Japan
We succeeded in the generation of tetraphenyldilithiostannole 1a,[1] and its considerable aromatic
character was established by X-ray diffraction analysis and theoretical calculations.[2] The lead
analog, tetraphenyldilithioplumbole 2 was also found to be aromatic, indicating that the concept of
aromaticity is expanded to lead-bearing carbon cycles.[3]
After the synthesis of heavier congeners of Cp anion, attention was next paid to the preparation of
transition-metal complexes with such heavier Cp ligands. The first heavier metallocene was a
ruthenocene bearing a germole ligand,[4] and transition-metal complexes with silole and germole
ligands have already been synthesized. The straightforward method for the synthesis of such
metallocenes is the reactions of metallole anions and dianions with transition-metal reagents.
However, the reactions using stannole anions and dianions had never been reported until recently.
We examined the reaction of tetraphenyldilithiostannole 1b[5] with [Cp*RuCl]4, and butterfly
complex 3 was obtained instead of an expected ruthenocene.[6] The reaction of 1b with Cp2TiCl2
afforded three-membered ring compound 4 with unique electronic states.[7] The synthesis of the first
neutral triple-decker complex 5 with group 14 metallole ligands was also achieved using silylsubstituted dilithiostannole 1c.
R2
Li
R1
M
R2
Li
1a:
1b:
1c:
2:
M =Sn;
M =Sn;
M =Sn;
M =Pb;
Et
Ru
Et
Ru
2
R =R =Ph
R 1=R 2=Et
R 1 = M e 3 S i, R 2 = P h
1
2
R =R =Ph
Ph
Et
Sn
Cp
Sn
Et
R1
1
Et
Et
Sn
Et
Cp* Et
Ti
Cp
Sn
Ph
RuCp*
S iM e 3
C p *R u
M e3S i
Sn
Cp*
4
3
5
References
[1] Saito, M.; Haga, R.; Yoshioka, M. Chem. Commun. 2002, 1002.
[2] Saito, M.; Haga, R.; Yoshioka, M.; Ishimura, K.; Nagase, S. Angew. Chem., Int. Ed. 2005, 44,
6553.
[3] Saito, M.; Sakaguchi, M.; Tajima, T.; Ishimura, K.; Nagase, S.; Hada, M. Science 2010, 328,
339.
[4] Freeman, W. P.; Tilley, T. D.; Rheingold, A. L.; Ostrander, R. L. Angew. Chem., Int. Ed. Engl.
1993, 32, 1744.
[5] Saito, M.; Kuwabara, T.; Kambayashi, C.; Yoshioka, M.; Ishimura, K.; Nagase, S. Chem. Lett.
2010, 39, 700.
[6] Kuwabara, T.; Saito, M.; Guo, J. D.; Nagase, S. Inorg. Chem. 2013, 52, 3585.
[7] Kuwabara, T.; Guo, J. D.; Nagase, S.; Saito, M. Angew. Chem., Int. Ed. 2014, 53, 434.
46
IL24
NEW METHODS FOR PEROXIDE SYNTHESIS
A.O. Terentev
ZIOCh, Moscow, Russia
In the last decades, organic peroxides have received considerable attention from chemists and drug
design experts, which is associated with a need in the search for drugs for the treatment of parasitic
diseases, such as malaria and helminth infections. Considerable progress has been made in the
design of effective peroxide antimalarial drugs. Some synthetic peroxides exhibit activity equal to
or higher than that of artemisinin. Peroxides having antitumor or growth-regulatory activity were
also documented. In our work we developed new methods for synthesis of various types of
peroxides.
It was found that some peroxides posesses pronounced antischistosomal properties and anticancer
activity. This work is supported by the Grant of the Russian Foundation for Basic Research (Grant
14-03-00237) and by the Program for Basic Research of the Presidium of the Russian Academy of
Sciences.
References
[1] Terent'ev, A., Borisov, D., Yaremenko, I., Chernyshev, V., Nikishin, G. J.Org.Chem. 75, 50655071, 2010.
[2] Terent'ev, A., Yaremenko, I., Chernyshev, V., Dembitsky, V., Nikishin, G. J.Org.Chem. 77,
1833-1842, 2012.
[3] Ingram, K., Yaremenko, I.A., Krylov, I., Hofer, L., Terent'ev, A. O., Keiser, J. J.Med.Chem. 55
(20), 8700–8711, 2012.
[4] Terent'ev, A. O., Yaremenko, I, A., Vil', V. A., Dembitsky, V. M., Nikishin, G. I. Synthesis
246-250, 2013.
[5] Terent'ev, A. O., Yaremenko, I, A., Vil', V. A., Моisееv, I. K., Kon’kov, S. A., Dembitsky, V.
M., Levitsky, D. O., Nikishin, G I. Org. Biomol. Chem. 11, 2613–2623, 2013.
[6] I.A. Yaremenko, A.O. Terent’ev, V.A. Vil’, R.A. Novikov, V.V. Chernyshev, V.A. Tafeenko,
D.O. Levitsky, F. Fleury, G.I. Nikishin. Chemistry - A European Journal DOI:
10.1002/chem.201402594.
47
IL25
SYNERGISM BETWEEN THEORY AND EXPERIMENTS IN
ASYMMETRIC CATALYSIS: TRANSITION STATE MODELING FOR
RATIONALIZATIONS AND CATALYST DESIGN
R.B. Sunoj
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076
Computational quantum chemistry has been increasingly employed toward rationalizing the
stereochemical outcome of a diverse range of reactions.1 The approach typically involves the
identification of kinetically significant transition states and intermediates. In our laboratory, ab
initio as well as DFT methods are employed to gain insights into carbon-carbon and carbonheteroatom bond-forming reactions of immediate practical significance.2 The key objective is in
establishing the factors responsible for stereoselectivity in such reactions and to employ those
insights toward in silico design of novel catalysts for potential asymmetric applications.3
A number of examples wherein the conventional transition state models required systematic
improvements toward accounting the observed product distribution and stereochemical outcome
will be presented. In general, the presentation would encompass a few contemporary themes in the
domain of organo- and organo-metallic catalysis. Interesting interpretations/rationalizations of
experimental observations besides meaningful guidelines for rational improvements in asymmetric
catalysis would remain the key focus of the presentation. The contents are designed to cater to a
broad and diverse group of audience; hence, the chemical insights would receive more emphasis,
rather than intricate technical details.
[1] (a) Cheong, P. H. –Y.; Legault, C. Y.; Um, J. M.; Celebi-Olcum, N.; Houk, K. N. Chem. Rev.
2011, 111, 5042. (b) Sunoj, R. B. Wiley Interdisciplinary Reviews: Comput. Mol. Sci. 2011, 1,
920.
[2] (a) Shinisha, C. B.; Sunoj, R. B. J. Am. Chem. Soc. 2010, 132, 12135. (b) Sharma, A. K.;
Sunoj, R. B. Angew. Chem. Int. Ed. 2010, 49, 9373. (c) Sharma, A. K.; Sunoj, R. B. Chem.
Commun. 2011, 47, 5759. (d) Jindal, G.; Sunoj, R. B., Chem. Eur. J. 2012, 18, 7045. (e) Jindal,
G.; Sunoj, R. B., Angew. Chem., Int. Ed. 2014, 53, 4432. (f) Anand, M.; Sunoj, R. B.; Schaefer,
H. F. J. Am. Chem. Soc. 2014, 136, 5535.
[3] (a) Shinisha, C. B.; Sunoj, R. B. Org. Biomol. Chem. 2007, 5, 1287. (b) Shinisha, C. B.; Sunoj,
R. B. Org. Lett. 2009, 11, 3242. (c) Jindal, G.; Sunoj, R. B. Org. Bimol. Chem. 2014, 12, 2745.
48
IL26
CATALYTIC ASYMMETRIC CROTYLATION: METHOD DEVELOPMENT
AND APPLICATION IN TOTAL SYNTHESIS
A.V. Malkov, P.S. O’hora, C.A. Incerti-Pradillos, M.A. Kabeshov
Loughborough University, Loughborough, LE11 3TU, UK
Secondary metabolites 1-5 isolated from marine soft coral Pseudopterogorgia elisabethae exhibit a
wide range of useful biological properties, which include anti-tubercular, anti-inflammatory,
antimicrobial and analgesic activities [1]. The analgesic properties are superior to the existing
industry standards. As a result, partially purified gorgonian extracts are used in commercial skin
care products for topical applications [2].
O
H
O
OH
HO
O
H
O
OH
HO
O
HO
H
H
H
O
H
H
1
2
3
4
(+)-Elisabethadione (–)-Elisapterosin B (–)-Colombiasin A
(+)-Erogorgiaene
5
Pseudopterosin A-D
aglycone
Herein, we present a novel general strategy for a scalable enantioselective total synthesis of
serrulatane diterpenes 1 and 2. Synthetically, a major challenge associated with the synthesis of
these compounds is the control of the three stereocentres in the absence of directing functional
groups. Our principal strategy is based on the asymmetric crotylation of cinnamyl-type aldehyde 10
with Z-crotyltrichlorosilane 9 to produce homoallylic alcohol 8 with a set of stereogenic centers that
will be used to control the stereochemistry of oxy-Cope rearrangement (8 → 7) and the subsequent
transformations towards the advanced intermediate 6. Development of novel efficient Lewis base
catalysts for the asymmetric crotylation and completion of the total synthesis of (–)-elisabethadione
and (–)-erogorgiaene will be discussed in detail.
cationic cyclisation
1
H
H
4
1,2
11
Rn
Wittig
olefination
Rn
Anionic
oxy-Cope
OH
6
O
7
OH
O
Rn
10
SiCl3
9
Rn
Cat*
References
[1] A. D. Rodriguez, C. Ramirez, J. Nat. Prod. 2001, 64, 100-102.
[2] A. Kijjoa , P. Sawanwong, Mar. Drugs 2004, 2, 72-82.
49
8
IL27
SYNTHESES OF METAL COMPLEXES WITH TRANS-CYCLOALKANE1,2-DIYL-[OSSO]-TYPE BIS(PHENOLATE) LIGAND AND ISOSPECIFIC
POLYMERIZATION OF ALPHA-OLEFINS
A. Ishii
Department of Chemistry, Graduate School of Science and Engineering, Saitama University,
Shimo-okubo, Sakura-ku, Saitama 338-8570, Japan
Efficiency and stereoselectivity of reactions catalyzed by metal complexes are often greatly affected
by auxiliary ligands of the catalysts. We have recently developed tetradentate auxiliary ligands 1
featuring oxygen and sulfur coordination sites and fusion of trans-cycloalkane-1,2-diyl rings.1–3 The
[OSSO]-bis(phenolate) ligand 1 (n = 3) was applied to the synthesis of zirconium complex 2 and we
found that a combination of 2 and an activator catalyzes the polymerization of 1-hexene with high
activity and high isospecificity1 in comparison with previously reported group 4 metal complexes
bearing [OSSO]-type ligands.4 We have also synthesized Ti,5 Zr,6 Hf,7 V,8 Nb,8 Ta,8 and Al9
complexes with 1 (n = 3) and investigated catalytic reactions with these complexes. In this paper,
we report the syntheses and structures of these metal complexes and their catalytic ability with
recent progress.
tBu
tBu
tBu
OH
S
tBu
O
S
Zr
n
S
S
O
OH
1
Bu
CH2Ph
2/(Ph3C)[B(C6F5)4]
activity =
2,500 g•mmol–1•h–1
tBu
tBu
tBu
CH2Ph
Bu
Bu
Bu
Bu
Bu
isotactic poly(1-hexene)
([mmmm] >95%)
Mw = 59,000, PDI = 1.7
tBu
2
References
1. Ishii, A.; Toda, T.; Nakata, N.; Matsuo, T. J. Am. Chem. Soc. 2009, 131, 13566–13567.
2. Ishii, A.; Toda, T.; Nakata, N.; Matsuo, T. Phosphorus, Sulfur, Silicon 2011, 186, 1169–1174.
3. Ishii, A.; Asajima, K.; Toda, T, Nakata, N. Organometallics 2011, 30, 2947–2956.
4. Nakata, N.; Toda, T.; Ishii, A. Polym. Chem. 2011, 2, 1597–1610.
5. Nakata, N.; Toda, T.; Matsuo, T.; Ishii, A. Inorg. Chem. 2012, 51, 274–281.
6. Toda, T.; Nakata, N.; Matsuo, T.; Ishii, A. J. Organomet. Chem. 2011, 696, 1258–1261.
7. Nakata, N.; Toda, T.; Matsuo, T.; Ishii, A. Macromolecules 2013, 46, 6758–6764; Nakata, N.;
Saito, Y.; Watanabe, T.; Ishii, A. Top. Catal. 2014, 57, 918–922.
8. Toda, T.; Nakata, N.; Matsuo, M.; Ishii, A. ACS Catal. 2013, 3, 1764−1767.
9. Nakata, N.; Saito, Y.; Ishii, A. Organometallics 2014, 33, 1840–1844.
50
IL28
NEW APPROACH FOR THE SYNTHESIS OF COMPOUNDS CONTAINING
CF2 FRAGMENT
A.D. Dilman, V.V. Levin, A.A. Zemtsov, M.D. Kosobokov
N. D. Zelinsky Institute of Organic Chemistry
Existing methods for the synthesis of compounds containing CF2 fragment either employ hazardous
reagents or require long synthetic sequence. We propose a new approach towards difluorinated
compounds based on the coupling of three components — nucleophile, difluorocarbene and
electrophile.
As nucleophiles, organometallic reagents can be employed. The insertion of difluorocarbene into
carbon-zinc bond of organozinc reagents leads to new organozinc species, which can be quenched
by halogen or proton,1 or coupled with allylic electrophiles.2
The interaction of trimethylsilyl cyanide with difluorocarbene affords difluoro(trimethylsilyl)acetonitrile. This reagent was used in reactions with aldehydes and imines furnishing fluorinated
alcohols and amines.3 The addition products can be transformed into a variety of heterocyclic
molecules.4
This work was supported by the Ministry of Science (project MD-4750.2013.3) and Russian
Foundation for Basic Research (projects 13-03-12074, 14-03-00293, 14-03-31253_mol_a, 14-0331265_mol_a).
1. Levin, V. V.; Zemtsov, A. A.; Struchkova, M. I.; Dilman, A. D. Org. Lett. 2013, 15, 917–919.
2. Zemtsov, A. A.; Kondratyev, N. S.; Levin, V. V.; Struchkova, M. I.; Dilman, A. D. J. Org.
Chem. 2014, 79, 818–822.
3. Kosobokov, M. D.; Dilman, A. D.; Levin, V. V.; Struchkova, M. I. J. Org. Chem. 2012, 77,
5850–5855.
4. Kosobokov, M. D.; Struchkova, M. I.; Arkhipov, D. E.; Korlyukov, A. A.; Dilman, A. D.
J. Fluorine Chem. 2013, 154, 73–79.
51
IL29
TOWARDS REALISTIC FIRST-PRINCIPLES MODELLING OF
COMPLEXITY IN HETEROGENEOUS CATALYSIS
K.M. Neyman
ICREA and Universitat de Barcelona
Active components present in heterogeneous catalysts as nano-aggregates of thousands atoms
remain inaccessible for the first-principles (based on DFT) computations due to their size and
complexity. However, such species could be rather realistically represented by computationally
tractable smaller model nanoparticles (NPs), whose surface sites only marginally change the
reactivity with increasing particle size. We illustrate this for decomposition of methane1 and
methanol2-4 on Pt and Pd catalysts as well as building of active sites on Pt/ceria catalysts. 5,6 We
show that using common slab models and thus neglecting the nanoscopic effects in these and
similar systems could lead to severe misrepresentation of the surface reactivity.7
Methane decomposition on Pt NP is calculated to be more exothermic than on Pt(111) surface and
proceed via much lower activation barriers for the rate-limiting steps.1 The reason for Pt activation
by nanostructuring is that CHx species are stabilized on NP edges, converting the first two steps of
CH4 decomposition from endothermic on Pt(111) to exothermic on Pt79. The higher activity of edge
Pt atoms was assigned to their lower coordination and higher flexibility.
The flexibility affects not only adsorption properties of sites with low-coordinated atoms but also
nearby terrace sites. This effect is most pronounced for strongly bound adsorbates, e.g atomic C. It
is a common by-product in decomposition reactions on Pd,2 able to modify catalyst properties upon
exothermic migration subsurface.3,4 The most spectacular effect of flexibility of Pd NPs is on the
subsurface migration barriers of surface C. Near NPs edges these barriers essentially vanish.
Presence of subsurface C makes Pd NPs more transparent for subsurface diffusion of adsorbed
hydrogen,3 which in turn enables sustainable hydrogenation of olefins on Pd catalysts.
Strong metal-support interactions can radically modify surface chemistry. Due to catalysts
complexity the microscopic origin of such effects is usually unresolved. However, our study on
models of Pt-ceria catalysts succeeded to uncover atomic details of interactions in this system. 5
Calculations identified two types of oxidative Pt-ceria interactions: electron transfer from a Pt
particle to the support and O transport from ceria to Pt. The former is favorable on ceria supports
regardless their morphology. But the O transfer requires the presence of Pt in close contact with
nanostructured ceria, being inherently a nano-effect. Both effects were detected by monitoring the
Ce3+/Ce4+ ratio using resonant photoelectron spectroscopy on Pt-CeO2 model catalysts.
These case studies reveal very significant differences in the surface reactivity derived from
customary slab-model calculations and those employing dedicated NP models. The latter expose a
variety of active sites, whose structure and geometric flexibility notably better match those of the
sites present under experimental conditions. Thus, we advocate much broader usage of suitable NP
models in “catalysis from first principles”.
1. F. Viñes, Y. Lykhach, T. Staudt, M. P. A. Lorenz, C. Papp, H.-P. Steinrück, J. Libuda, K. M. Neyman, A. Görling Chem. Eur. J. 2010, 16, 6530.
2. I. V. Yudanov, A. V. Matveev, K. M. Neyman, N. Rösch - J. Am. Chem. Soc. 2008, 130, 9342.
3. K. M. Neyman, S. Schauermann - Angew. Chemie Int. Ed. 2010, 49, 4743.
4. H. A. Aleksandrov, F. Viñes, W. Ludwig, S. Schauermann, K. M. Neyman - Chem. - Eur. J. 2013, 19, 1335.
5. G. N. Vayssilov, Y. Lykhach, A. Migani, T. Staudt, G. P. Petrova, N. Tsud, T. Skála, A. Bruix, F. Illas, K. C. Prince,
V. Matolín, K. M. Neyman, J. Libuda - Nature Mater. 2011, 10, 310.
6. A. Bruix, Y. Lykhach, I. Matolínová, A. Neitzel, K. C. Prince, V. Potin, F. Illas, V. Matolín, J. Libuda, K. M.
Neyman, et al. - Angew. Chemie Int. Ed. 2014, 53, doi: 10.1002/anie.201402432.
7. S. M. Kozlov, K. M. Neyman - Top. Catal. 2013, 56, 86.
52
IL30
С-С TRIPLE BOND ACTIVATION BY PLATINUM METALS UNDER
HOMO- AND HETEROGENEOUS CONDITIONS: DESIGN OF NEW
CATALYTIC REACTIONS
S.A. Mitchenko
L.M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences
of Ukraine, Donetsk, Ukraine
Petroleum and natural gas are the main sources of raw materials for modern bulk and fine chemical
industry. Since the middle of the last century this changed the industry redirecting technology
previously based on acetylene towards olefinic stuff and synthesis gas. Nevertheless, series of largescale (for example, manufacture of vinyl ethers, pyrrolidone and N-methylpyrrolidone, butanediol,
etc.) and fine (drugs and fragrances, crop protecting agents, etc.) chemical production based on
acetylene hydrocarbons possesses definite advantages and is still developing. Besides, acetylene
hydrocarbons are inevitably formed as by-products in oil processing yielding olefins, and taking
into account the modern industrial scales and prices of starting materials these by-products should
be efficiently utilized. On the other hand, coal and natural gas supply as against of petroleum allow
us to regard them as practically inexhaustible source of acetylene. Increasing interest to the catalytic
chemistry of acetylene (see, for example, [1, 2]) can be motivated in particular by these
considerations.
Results of development of new catalytic transformations of acetylene under homo- and
heterogeneous conditions will be presented and discussed.
References:
1. Alonso F., Beletskaya I.P., Yus M. Chem. Rev., 2004, 104, 3079.
2. Ananikov V. P., Beletskaya I. P. Organometallics, 2012, 31, 1595.
53
IL31
SYNERGISTIC EFFECTS IN DESIGNING COMBINED CATALYTIC
SYSTEMS (COMBICAT’S) FOR ABATEMENT OF
NITROGEN OXIDES (NOX)
A.Yu. Stakheev
Zelinsky Institiute of Organic Chemistry, Catalysis division, Moscow, Russia
Anthropogenic emission on nitrogen oxides (NOx = NO, NO2, N2O) becomes an important issue,
since the amount of anthropogenic NOx nowadays exceeds biogenic emission (~110 Mt vs. 80
Mt/annual) and their impact on environment is significant. The most effective method for
abatement of nitrogen oxides is their selective catalytic reduction (SCR) by urea or NH3:
2NO + 2NH3 + 1/2O2 = 2N2 + 3 H2O
However, activity of the traditional NH3-SCR catalysts at the temperatures below 250oC is not
sufficient due to the stringent restrictions imposed by environmental legislations on NOx emission
from mobile sources. The effective solution can be provided by Cu-containing zeolite catalyst,
however high cost often limits their practical application. Our recent study revealed alternative
approach and indicated that promising NH3-DeNOx activity at Treact. < 250°C CAN BE ATTAINED OVER
combined catalysts (CombiCat) comprising zeolite component (possessing high activity in SCR)
and a redox component (having high activity in NO oxidation). For such compositions we found a
pronounced synergistic effect and the catalytic activity of the COMBICAT’S significantly exceeds
activity of the individual components. A number of compositions have been tested for searching
synergistic effects and the most remarkable results have been observed for [Cu/Al2O3 +FeBETA],
[Mn/Al2O3 + FeBETA, [CeZr +FeBETA], [Mn/CeZr + FeBETA], Mn/FeBETA. Interestingly that
the studied composition exhibits favorable performance in selective oxidation of NH3:
2NH3 + 3/2 O2 = N2 + 3H2O
Therefore CombiCat’s are capable to accomplish two functions: SCR catalyst and removal of
residual NH3. In addition to that, for the compositions comprising CeO2-ZrO2 component a
promising soot oxidation activity has been observed
Detailed study of a possible origin of the observed synergistic effects suggests that the improvement
of NH3-DeNOx activity can be attributed to a “dual function” reaction mechanism comprising two
main stages:
(1) NO + O2 ↔ NO2
over redox component
(2) NO + NO2 + 2NH3 → N2 + 3H2O
over zeolite component
However, further research is required for revealing overall reaction network and understanding
reaction mechanism responsible for observed synergy.
54
IL32
NOVEL COLCHICINOIDS AS POTENTIAL ANTITUMOR AGENTS
A. Yu. Fedorov
Department of Organic Chemistry, Nizhny Novgorod State University, Gagarina av. 23, Nizhny
Novgorod 603950, Russian Federation
A range of indole - and furane-containing allocolchicinoids was synthesized:
Several from synthesized compounds manifested high in vitro and in vivo antitumor activity.
Acknowledgment
We thank the Russian Foundation for Basic Research (projects 14-03-91342 and 12-03-00214-a),
The Ministry of Education and Science of The Russian Federation (project 4.619.2014/K). The
research is partly supported by the grant № 02.В.49.21.0003 of The Ministry of Education and
Science of the Russian Federation to Lobachevsky State University of Nizhni Novgorod.
55
IL33
ENANTIOSELECTIVE CATALYSIS BY CHIRAL BRØNSTED ACIDS AND
CHIRAL BRШNSTED BASES
M. Terada
Tohoku Univsersity, Department of Chemistry, Sendai, Japan
Chiral phosphoric acids 1 have become one of the most versatile types of chiral Brønsted acid
catalysts identified to date and have been applied to a broad range of enantioselective
transformations.1,2) In my continuing efforts to broaden the scope of enantioselective catalysis by 1,
activation of oxygenated functional groups other than imines and related functional groups is our
recent research interest. To expand the scope of chiral Brønsted acid catalysis, recently a novel
chiral bis-phosphoric acid 2 was developed as a highly active and efficient enantioselective
catalyst.3) On the other hand, intense interest has been devoted to the development of chiral
uncharged organosuperbase catalysts during the past decade. In an effort to develop efficient chiral
organobase catalysts, we designed and synthesized unique axially chiral Brønsted base 3.4) 3
functioned as the efficient enantioselective catalysts for the activation of pro-nucleophile having a
relatively acidic proton such as 1,3-dicarbonyl compounds. To expand the scope of chiral Brønsted
Base catalysis, development of much stronger organosuperbase is highly demanded. We hence
designed a pseudo C2-symmetric bis(guanidino)iminophosphorane 4 as a novel family of chiral
organosuperbases.5) In my presentation, I briefly introduce these chiral Brønsted acid catalysts (1
and 2) and base catalysts (3 and 4). In particular, I would like to present a novel chiral Brønsted
base catalyst 4 in details.
References
1) (a) Terada, M. Synthesis 2010, 1929-1982. (b) Terada, M. Chem. Commun. 2008, 4097-4112.
2) Uraguchi, D.; Terada, M. J. Am. Chem. Soc. 2004, 126, 5356-5357.
3) Momiyama, N.; Konno, T.; Furiya, T.; Iwamoto, T.; Terada, M. J. Am. Chem. Soc. 2011, 133,
19294-19297.
4) Terada, M.; Ube, H.; Yaguchi, Y. J. Am. Chem. Soc. 2006, 128, 1454-1455.
5) Takeda, T.; Terada, M. Y. J. Am. Chem. Soc. 2013, 135, 15306-15309.
56
IL34
IONIC LIQUIDS, WATER AND LIQUID OR SUPERCRITICAL CO2 AS
PERSPECTIVE MEDIA FOR ASYMMETRIC ORGANOCATALYSIS
S.G. Zlotin
N.D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences
Over the last decade amazing results have been associated with the extensive application of
asymmetric organocatalysts in organic synthesis. In the presence of small metal-free chiral organic
molecules (α-amino acid or cinchona alkaloid derivatives, BINOL phosphoric acids, and other
chiral compounds), available prochiral reagents can be easily converted into chiral products of high
molecular complexity in high yields and with excellent enantioselectivities. Unlike organometal
catalysts, organocatalysts do not contaminate products with toxic heavy metals and this is important
in terms of medicinal chemistry. However, in some cases they may be responsible for hardly
separable and potentially dangerous organic impurities.
To facilitate product purification and recovery of precious chiral catalysts, immobilized forms of
organocatalysts tagged to polymers or ionic groups have been designed and organocatalytic
reactions have been carried out in so called “neoteric” green solvents, particularly in ionic liquids
(IL), water and liquid or supercritical (sc) carbon dioxide. In these systems a catalyst and a product
are located in different phases during the catalytic process and/or the working-up step.
We developed highly efficient enantioselective cross-aldol reactions between various carbonyl
compounds in the presence of proline or prolinamide-derived organocatalysts in the IL and/or
aqueous environment. An original method for adapting -amino acid-sourced IL-supported chiral
organocatalysts to the aqueous medium via an incorporation of long-chain alkyl groups and
hydrophobic anions into their molecules and by performing asymmetric reactions in reagents/water
two-phase systems was elaborated. Corresponding aldol products were obtained in high yields and
with extremely high anti -diastereo- (dr up to 98 : 2) and enantioselectivities (ee up to 99%) under
proposed conditions. After product isolation, the remaining catalyst-water heterogeneous system
could be reused up to 15 times without a decrease of product yield and selectivity of the reaction.1
Carbon acids, in particular malonates, malononitrile, and anthranone, appeared to react
enantioselectively with nitroalkenes in the presence of tertiary amine/thiourea-derived bifunctional
organocatalyst in liquid CO2 as a green substitute of toxic organic solvents to afford the respective
Michael adducts in moderate to high yields and with enantioselectivities of up to 92% ee.2 The first
“green” asymmetric organocatalytic reaction in sc-CO2, namely, a bifunctional squaramidecatalyzed addition of diphenylphosphite to α-nitroalkenes to afford β-nitrophosphonates in high
yields and with ee-values of up to 94% was elaborated.3 In this way, the most active (R)-enantiomer
of the therapeutically useful GABAB receptor agonist baclofen, a key precursor of the chiral
anticonvulsant, pregabalin, and both enantiomers of pharmacologically important β-amino
phosphonic acid derivatives were synthesized. A significant potential of the supercritical extraction
for product isolation and catalyst recovery, which completely eliminates the use of organic solvents
during the working-up procedure, was demonstrated.
The work was financially supported by the Russian Foundation of Basic Research (projects 12-0300420, 14-03-31321 and 14-03-92701).
1. D.E. Siyutkin, A.S. Kucherenko, S.G. Zlotin. In “Comprehensive Enantioselective
Organocatalysis: Catalysts, Reactions, and Applications”, ed. by P.I. Dalco, Wiley-VCH, 2013,
v. 2, p. 617-650.
2. A.G. Nigmatov, I.V. Kuchurov, D.E. Siyutkin, S.G. Zlotin. Tetrahedron Lett., 2012, 53, 3502.
3. I.V. Kuchurov, A.G. Nigmatov, E.V. Kryuchkova, A.A. Kostenko, A.S. Kucherenko, S.G.
Zlotin. Green Chem., 2014, 16, 1521.
57
IL35
MAKING OLEFIN METATHESIS WORK - RECENT RESULTS IN
RUTHENIUM CATALYSTS DESIGN
K.L. Grela
Biological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw
Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful
transformation for the formation of new carbon-carbon double bonds [1]. This area is now quite
familiar to most chemists as numerous catalysts are available that enable a plethora of olefin
metathesis reactions [1]. However, formation of substituted and crowded double bonds, decreasing
the amount of metal, using metathesis in green context, etc. still remain a challenge, making
industrial applications of this methodology difficult [2]. These limitations can be solved by
designing new, more active and stable catalysts and catalysts that can be easier removed / recycled
[3].
During the lecture a number of representative examples will be presented.
Artwork © Katarzyna Felchnerowska, www.fb.com/effe.fineart
References
[1] Olefin Metathesis: Theory and Practice, Grela, K. (Ed.), John Wiley & Sons, 2014
[2] Thayer, A. Chemical & Engineering News 2007, 85 (07), 37.
[3] Clavier, H.; Grela, K.; Kirschning, A.; Mauduit, M.; Nolan, S. P. Angew. Chem. Int. Ed. 2007,
46, 6786-6801
58
59
Oral Communications
60
61
OC1
THE FIRST CYCLOPENTADIENYL NICKEL COMPLEXES BEARING A
SILYL GROUP OR HYDROGEN SUBSTITUTED PHOSPHINE
CHELATING SIDECHAIN
I. Werner, H. Butenschoen
Institute of Organic Chemistry, Leibniz Universitaet Hannover, Hannover, Germany
The only known secondary phosphine pendant cyclopentadienyl complexes are those of zirconium
and hafnium, reported by Ishiyama et al. in 2002.[1] Since these complexes contain a reactive
phosphorus-hydrogen bond, they were converted into the corresponding phosphide-substituted
cyclopentadienyl chelate complexes.[2] Both systems were successfully applied in catalytic ethylene
and styrene polymerization reactions as well as in ethylene/styrene copolymerization reactions.[3]
To our knowledge, no analogous complexes of late transition metals containing a phosphorushydrogen or a phosphorus-silyl bond have so far been reported. We report on the synthesis of the
first cyclopentadienyl nickel complexes 1-4 and 5, 7 bearing a silyl group and hydrogen substituted
phosphine chelating sidechain, respectively.
Treatment of complex 5 with SIMes induced the decomplexation of the secondary phosphane
substituted tether, delivering exclusively nickel carbene complex 6.
Recrystallization of complex 7 from hexane/ethyl acetate (1:1) at 30 °C afforded crystals suitable
for an X-ray crystal structure analysis.
References:
[1] T. Ishiyama, H. Nakazawa, K. Miyoshi, J. Organomet. Chem. 2002, 648, 231.
[2] T. Ishiyama, T. Mizuta, K. Miyoshi, H. Nakazawa, Organometallics 2003, 22, 1096.
[3] T. Ishiyama, K. Miyoshi, H. Nakazawa, J. Mol. Cat. A-Chem. 2004, 221, 41.
62
OC2
EXPANDED RING N-HETEROCYCLIC CARBENE TRANSITION METAL
COMPLEXES. SYNTHESIS, STRUCTURE, APPLICATIONS IN
CATALYSIS
M.S. Nechaev1, A.F. Asachenko2, P.B. Dzhevakov2, O.S. Morozov2, G.V. Proskurin1, P.S.
Gribanov1
1 - Moscow State University, Department of Chemistry, Moscow, Russia
2 - A. V. Topchiev Institute of Petrochemical Synthesis, RAS, Moscow, Russia
N-heterocyclic carbenes (NHCs) became widely used as organocatalysts and as ligands in transition
metal catalysis. Most of NHC-metal complexes known to date are derived from five-membered ring
imidazol-2-ylidene and imidazolin-2-ylidene type carbenes. In recent years, our group develops
chemistry of 6-, 7- and 8-membered ring carbenes. Expanded ring carbenes (er-NHCs) exhibit
superior stereoelectronic properties in comparison with five-membered ring counterparts.
Expansion of the ring leads to significant increase in donor strength and sterical hindrance.
In this contribution we report our recent results on theoretical calculations of electronic structure
and ligand properties of er-NHCs; efficient methods of synthesis of precursors and generation of
free carbenes; synthesis of late transition metal (Cu, Ag, Au, Pd) complexes. It was found that erNHC complexes of palladium are highly active in Suzuki-Miyaura coupling in water, and
dimerization of terminal alkynes with formation of E-enynes. Cationic gold complexes are active
catalysts of addition of nucleophiles to carbon-carbon triple bonds.
63
OC3
PALLADIUM-CATALYZED C–H ALKENYLATION OF ARENES USING
SULFUR-CONTAINING DIRECTING GROUPS: A COMPARATIVE STUDY
K.V. Luzyanin, A.N. Marjanov, V.P. Ananikov
Laboratory of Cluster Catalysis, Saint Petersburg State University, Universitetsky pr. 26, Stary
Petergof, 198504, Russia
Direct alkenylation of organic substrates via directing-group assisted functionalization of the CH
bond has emerged as a valuable tool for creation of new sp2-sp2 bonds. In the contrast to the
Mirozoki–Heck reaction that starts from the aryl halides, this procedure works with inactivated
arenes and is favorable from both economical and environmental points of view. Several types of
directing groups have been evaluated in the direct alkenylation up to date, e.g., ketones and
carboxylates, amides, pyridine sulfoxides and ethers, and thioethers. Among them, functionalization
of sulfur-containing compounds (Scheme 1), i.e. pyridine thioesters and sulfoxides, as well as
structurally related benzylic thioethers (in those, sulfur moiety plays a role of a directing group)
attracts rapidly growing attention. On the one hand, functionalization of such compounds leads to
interesting derivatives containing both alkene and sulfur functions, while, on the other hand, sulfurbased directing groups in these species can be easily removed after reaction from the resulting
products without compromising other functionalities.1–3
Scheme 1. Direct alkenylation of arenes using sulfur-containing directing groups.
In the current report, we summarize data accumulated up to date regarding direct CH-alkenylation
of sulfur-containing organic compounds. A particular emphasis is given to the evaluation of the
assistance provided by different sulfur-containing directing groups in comparison to other common
directing moieties known to be employed for this purpose.
Acknowledgements: This work has been partially supported by the Saint Petersburg State
University (research grant from Laboratory of Cluster Catalysis), and the Russian Fund for Basic
Research (grant 14-03-01005).
References
1. García-Rubia, A.; Fernández-Ibánez, M. A.; Gómez Arrayás, R.; Carretero, J. C. Chem. Eur. J.
2011, 17, 3567–3570.
2. Yu, M.; Xie, Y.; Xie, C.; Zhang, Y. Org. Lett. 2012, 14, 2164–2167.
3. Zhang, X.-S.; Zhu, Q.-L.; Zhang, Y.-F.; Li, Y.-B.; Shi, Z.-J. Chem. Eur. J. 2013, 19, 11898–
11903.
64
OC4
IN PURSUIT OF A NOVEL IMIDATE-BASED SALEN-TYPE LIGAND
CLASS
J. Van Der Eycken1, P. Janssens1, T. Noel2
1 - Ghent University, Department of Organic Chemistry
2 - Eindhoven University of Technology, Department of Chemistry and Chemical Engineering,
Micro Flow Chemistry & Process Technology
An increasing ecological awareness and global competitiveness have challenged the chemical
industry towards a higher level of sustainability through innovation and technology. In research, the
majority of topics on sustainable process development deals with catalysis.[1] Furthermore, in
organic synthesis, transition metal catalysis already plays a vital role in the synthesis of biologically
active compounds.[2]
H
H
N
O H
N
H O
N
OH HO
N
OH
L1
HO
L2
Bisimidate ligand L2 shows striking similarities with Salen ligands (L1). We reasoned that this
could open new opportunities for our already well-established imidate ligand family. [3-5]
Nevertheless, the applicability of this ligand in the MnV-catalyzed asymmetric epoxidation reaction
turned out to be more complicated than expected.
In this communication, the search towards an effective novel imidate-based Salen-type ligand class
will be discussed from a ligand design point of view.
References
[1] Dichiarante, V.; Ravelli, D.; Albini, A. Green Chem. Lett. Rev. 2010, 3, 105.
[2] a) Noyori, R Angew. Chem. Int. Ed. 2002, 41, 2008. b) Busacca, C.A.; Fandrick, D.R.; Song,
J.J.; Senanayake, C.H. Adv. Synth. Catal. 2011, 353, 1825.
[3] a) Noël, T.; Bert, K.; Van der Eycken, E.; Van der Eycken, J. Eur. J. Org. Chem. 2010, 21,
4056. b) Bert K., Noël T., Van der Eycken J., Org. Biomol. Chem., 2012, 10, 8539. c) Noël, T.,
Bert, K., Janssens, P. and Van der Eycken, J. (2012) “Chiral Imidate Ligands: Synthesis and
Applications in Asymmetric Catalysis”, in: Innovative Catalysis in Organic Synthesis:
Oxidation, Hydrogenation, and C-X Bond Forming Reactions (ed P. G. Andersson), WileyVCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: 10.1002/9783527646586.ch14.
65
OC5
NITROALKANES IN PPA AS NEW REAGENTS FOR DIRECT METALFREE AMINATION OF ARENES
A.V. Aksenov1, N.A. Aksenov1, I.V. Aksenova1, M. Rubin2, D.A. Aksenov1
1 - Department of Chemistry, North Caucasus Federal University, Stavropol, Russian Federation
2 - Department of Chemistry, University of Kansas,Lawrence, USA
Aromatic amines represent an important class of organic compounds. Many of them demonstrate
important biological activities. Various multi-step methods for preparation of these compounds
have been developed, including electrophilic nitration/reduction sequence, Schmidt and Beckmann
rearrangements, etc. The most appealing methods, however, are those that allow for direct
introduction of an amino-group to a non-substituted arene over a single step.
Direct electrophilic acetamidation of arenes 2 with primary nitroalkanes 1 in polyphosphoric acid
(PPA), recently developed in our laboratories can be viewed as an example of such an approach.
R
R
R
R
N
+
N
O
PPA
+
4
OH
3
R
O
R
O
O
O
P
R
O ...
R O
3
N
2
2
OH
4
R
1
R
R
O ...
P
R
O
2
R
R
1
4
H
N
3
O
R
2
1
R
1
6 3 -9 2 %
3
R=Me, Pr, Ph, Bn; R1, R2, R3, R4=H, Me, OH, MeO, CHO.
Benzene and arenes with electron-donating substituents can be engaged in this reaction. Electron
deficient arenes are inert. The process is highly selective, the electrophilic attack is always directed
to para-position with respect to a substituent already present in the ring.
Anthracene 4 and indole 5 were successfully involved into the acetamidation reaction. In reaction of
dibenzo-18-crown-6 ether monoacetamide was formed along with quite a large amount of bisacetamination isomeric products.
The reaction involving secondary nitroalkanes is also interesting. Since the nitroso compound 4,
resulting from electrophilic attack to the aromatic ring, is not able to isomerize oxime, it attacks a
second molecule of arene. After rearrangement this leads to the formation of diarylamines 5:
R
1
+
R
2
N
+
O
R
-H+
1
N
O P O 2 H ...
R
-P P A
OH
O P O 2 H ...
2
R
1
N
-H2O
R
R
1
N
OH
1
N
R
R
1
R
2
R
1
H
N
R
1
2
R
OH
R
R
2
4
PPA
O
2
1
+
R
2
R
2
R
5
2
O
5 5 -6 1 %
R1, R2 =H, Me, MeO, CHO
A novel protocol for direct and regioselective metal-free acetamination and amination of arenes in
reactions with primary and secondary nitroalkanes in polyphosphoric acid media was developed. A
new preparative approach to 5-aminoindoles and diarylamines employing this reaction was
demonstrated.
This work was carried out with financial support from the Russian Foundation Basic Research
(grants 13-03-00304 a and 14-03-31288 mol_a)
66
OC6
UROTROPINE ISOMER (1,4,6,10-TETRAAZAADAMANTANE).
MOLECULAR SIMPLICITY AND MOLECULAR COMPLEXITY OF
HETEROADAMANTANE CAGE
A.Yu. Sukhorukov, A.N. Semakin, I.S. Golovanov, S.L. Ioffe, V.A. Tartakovsky
N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
For more than 100 years, heteroadamantanes have been objects of rapt attention for fundamental
and applied chemistry. These cage polycyclic systems represent interest not only due to their unique
properties, but also as convenient models for the study of basic problems dealing with structure and
reactivity of organic compounds. Among many heteroadamantanes, 1,3,5,7-tetraazaadamantane
(urotropine), which was first obtained by A. Butlerow in 1859, plays, probably, the most important
role from an applied point of view. Urotropine is widely used in medicine, polymer production,
food industry, as well as organic synthesis, coordination chemistry and MOFs design. This simplest
Td-symmetrical 1,3,5,7-tetraazaadamantane is the only known representative of the class of
tetraazaadamantanes. In this context the possibility of existence of other tetraazaadamantanes
isomeric to urotropine represents considerable fundamental interest.
The present report deals with the first synthesis of 1,4,6,10-tetraazaadamantane (“isourotropine”),
the C3v-symmetrical structural isomer of urotropine, and a series of its derivatives (see Figure). XRay and quantum-chemical studies demonstrate remarkable distinctions in structures of urotropine
and “isourotropine” cages, probably, arising from different types of lp(Neq)
*C N interactions in
these heterocage systems. Since substitution at bridge and bridgehead nitrogen atoms can be easily
installed, 1,4,6,10-tetraazaadamantane can be considered as a new rigid multivalent (3+1) scaffold
for the design of complex functional molecules and materials.
Acknowledgement
The financial support from RFBR (grant 14-03-00933a) and Russian President’s Council for Grants
(grant MK-3918.2013.3) is greatly acknowledged.
67
OC7
PALLADIUM-CATALYZED CROSS-COUPLING REACTION OF
ALCOHOL WITH ARYL CHLORIDE THROUGH C-C BOND ACTIVATION
C.-H. Jun, H.-S. Park, D.-S. Kim
Yonsei University, Department of Chemistry, Seoul, South Korea
The C-C bond activation is one of challenging subjects in organometallic chemistry.1 Especially
catalytic version of C-C bond activation has been recently achieved by chelation assisted transition
metal catalyst, consisted of Rh(I) and 2-amino-3-picoline.2 During the course of our studies on
these types of C-C bond activation, we found decarbonylative esterification of aliphatic alcohol
with aryl chloride by palladium metal as shown below. For example, when the reaction of
chlorobenzene and 1-naphtylethanol was carried out at 150oC under Pd/C and NaF base, a mixture
of three products, 1-naphtylethyl benzoate ester, benzene, and 1-methylnaphthalene, was obtained
in reasonable yields.
The reaction mechanism is proposed as follows. The reaction proceeds through several consecutive
reactions. Initially, primary alcohol is oxidized by aryl chloride to aldehyde with formation of arylH under palladium catalyst. Aldehyde is decarbonylated by Pd to generate alkane and (CO)Pd. The
intermediate (CO)Pd is oxidatively added to aryl chloride to form acyl-PdCl complex, which reacts
with alcohol to give ester compounds. In this reaction, reactivity of substrate should be well
balanced. The reactivity of chloroarene is suited for this purpose since other aryl halide such as
bromobenzene and iodobenzene did not show any reactivity in this reaction. This result is quite
interesting since aryl chloride is least reactive for common C-C bond coupling reaction while aryl
iodide is very reactive. The reaction works well with aryl chloride. One of merits in this protocol is
that carbonylation proceeds without using toxic CO gas, and CO source is non-toxic alcohol. More
detailed mechanistic studies using 13C-enriched or deuterated alcohol will be discussed.
References
1. Jun, C. -H. Chem. Soc. Rev. 2004, 33, 610-618.
2. Park, Y. J.; Park, J. -W.; Jun, C. -H. Acc. Chem. Res. 2008, 41, 222-234.
68
OC8
RADICAL-CATIONS OF ACETYLENE COMPOUNDS IN CARBONCARBON BOND FORMING REACTIONS
A.V. Vasilyev
Saint Petersburg State Forest Technical University, Institutsky per. 5, Saint Petersburg, 194021,
Russia; Saint Petersburg State University, Institute of Chemistry
Radical-cations of acetylene compounds A, generated under oxidation of alkynes I in systems
PbO2-strong acid (CF3CO2H, HF, HSO3F), are key reaction intermediates in various new carboncarbon bond forming processes [1-6].
Depending on structure, the species A lead to formation of a variety of products II-VII. When
substituents X are moderate electron acceptors CO2R, COAr, COR, PO(OEt)2, trans-ethenes II are
stereoselectively formed. In case of stronger acceptors, furan derivatives III (X = COCF3,
СОCO2Et), or diketones IV (X = CF3) are formed.
In different acidic systems radical-cations of diarylacetylenes (X = Ar) give unsaturated diketones
V (in CF3CO2H), butadiene difluiorides VI (in HF) or dichlorides VII (in HSO3F, followed by
quenching in HClaqua.,conc.). The last ones are electro-cyclically converted into naphthalenes VIII.
O
Cl
Ar
R
Ar
Ar
Ar
Ar
X = Ar
1. H+=HSO3F; 2. HCl
C C
Cl C
C Cl
VII
Ar C C X
A
X = Ar
F C
Ar
C F
Ar Ar
VI
X
O II
X = COCF3,
COCO2Et
X
C Ar
C C
Ar C
X = CF3
C
O
III
H+ = CF3CO2H
Ar
C C
Ar C
O
X = Ar
H+ = HF
Ar Ar
C Ar
C C
X = CO2Alk,
COAr, COMe,
PO(OEt)2
PbO2/H+
-e
VIII
Ar
X
Ar C C X
I
Ar
C C
Ar C
C Ar
O O
V
Y
Y = CF3,
CO2Et
F 3C
CF3
H C C H
Ar C
C Ar
O O
IV
[1] Vasilyev A.V., Rudenko A.P. Russ. J. Org. Chem. (in Engl.), 1997, V.33, P. 1555-1584.
[2] Shchukin A.O., Vasilyev A.V., Fukin G.K., Rudenko A.P. Russ. J. Org. Chem. (in Engl.),
2007, V.43, P.1446-1450.
[3] Vasilyev A.V., Aristov S.A., Fukin G.K., Kozhanov K.A., Bubnov M.P., Cherkasov V.K. Russ.
J. Org. Chem. (in Engl.), 2008, V.44, P. 791-802.
[4] Vasilyev A.V., Shchukin A.O., Walspurger S., Sommer J. Eur. J. Org. Chem., 2008, 4632.
[5] Vasilyev A.V., Rudenko A.P. Russ. J. Org. Chem. (in Engl.), 2010, V.46, P.1282-1289.
[6] Alkhafaji H.M.H., Vasilyev A.V., Ryabukhin D.S., Rudenko A.P., Muzalevskiy V.M.,
Nenajdenko V.G. Russ. J. Org. Chem. (in Engl.), 2013, V.49, P. 621-623.
69
OC9
ACTIVATION OF Ru-BASED OLEFIN METATHESIS CATALYSTS
A. Poater1, L. Cavallo2
1 - Institut de Quimica Computacional i Catаlisi and Departament de Quimica, Universitat de
Girona, Campus de Montilivi, E-17071 Girona, Catalonia, Spain
2 - Kaust Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University
of Science and Technology, Thuwal 23955-6900, Saudi Arabia
In recent years olefin metathesis catalyzed by N-heterocyclic carbene ruthenium complexes has
attracted remarkable attention as a versatile tool to form new C=C bonds.[1] The last developed
(pre)catalysts show excellent performances, and this achievement has been possible because of
continuous experimental and computational efforts to understand the laws controlling the behavior
of these systems. This perspective talk rapidly traces the ideas and discoveries that computational
chemistry contributed to the development of these catalysts, with particular emphasis on catalysts
presenting a N-heterocyclic carbene ligand. Specifically, one of the most important challenges in
ruthenium-catalyzed olefin metathesis is to increase the stability of the catalysts under reaction
conditions and this hopefully without loss of activity. Special interest has been addressed to study
the activation of the second-generation Grubbs catalysts, which has clarifier either a dissociative or
an interchange mechanism is feasible.[2]
Although, in the solid state, most ruthenium-based olefin metathesis catalysts are stable to oxygen
and moisture, in solution decomposition usually occurs readily. Understanding the decomposition
routes of catalysts is extremely important as any insight gained in this area can guide catalyst design
efforts, to participate then in the synthesis of drugs.[3,4] Furthermore, new challenging projects
plan to modify the structure of the NHC ligands, or replace this ligand by alkylidene ligands, and
even the substitution of the metal is a goal, moving to more environmentally friendly metals.
[1] G. C. Vougioukalakis, R. H. Grubbs, Chem. Rev. 110, 1746 (2010).
[2] C. A. Urbina-Blanco, A. Poater, T. Lebl, S. Manzini, A. M. Z. Slawin, L. Cavallo, S. P. Nolan,
J. Am. Chem. Soc. 135, 7073 (2013).
[3] S. Manzini, C. A. Urbina-Blanco, A. Poater, A. M. Z. Slawin, L. Cavallo, S. P. Nolan, Angew.
Chem. Int. Ed. 51, 1042 (2012).
[4] S. Manzini, A. Poater, D. J. Nelson, L. Cavallo, S. P. Nolan, Chem. Sci. 5, 180 (2014).
70
OC10
CHEMICAL REACTIVITY IN PROTEINS AND WATER: QM/MM MD
INSIGHTS INTO EFFECTS OF LOCAL STRUCTURAL ENVIRONMENTS
ON BOND CLEAVAGE
Y. Zhao, B.J. Wang, R.B. Wu, Z.X. Cao
Department of Chemistry, Xiamen University, Xiamen 361005, China
Water and proteins play a quite important role in chemical and biological processes. In past few
years, we carried out a systematic investigation on the effect of local structural environments on
reactivity towards hydrolysis, C-N, C-O, and C-H bond cleavages in proteins and water. Using
Born-Oppenheimer ab initio QM/MM MD simulations, a state-of-the-art approach to simulating
enzymes, we have investigated the structural features of zinc enzymes, nucleoside hydrolase, and
deaminase and plausible enzymatic mechanisms. The molecular complexity of active domain in
enzyme and roles of conserved residues and protein environments in enzymatic catalysis have been
explored. In particular, the different coordination modes and fast ligand exchanges of zinc
coordination has been suggested to be one key catalytic feature of the zinc ion, and the chelation
mode of hydroxamate with the zinc ion in HDACs is modulated by water access to the linker
binding channel. This new insight into the interplay between the linker binding and the zinc
chelation emphasizes its importance for the development of new class-IIa-specific HDAC
inhibitors. Our calculations indicate that the reliable theoretical treatment on the water-mediated
proton transfer and most hydrolysis reactions of carbonyl compounds, such as aldehydes, ketones,
esters, amides, the carboxylic acids, and their derivatives, requires use of the large basis set and
suitable cluster-continuum model. The effects of solvent and structural modification on hydration
and hydrolysis of carbonyl compounds have been discussed.
Acknowledgements. This work was supported by the National Science Foundation of China
(21133007 and 21373164) and the Ministry of Science and Technology (2011CB808504).
References
1. N Chen, H. Ge, J Xu, Z Cao, and R Wu, Biochim. Biophys. Acta 2013, 1834, 1117.
2. R Wu, W Gong, T Liu, Y Zhang, and Z Cao, J. Phys. Chem. B 2012. 116, 1984.
3. B Wang and Z Cao, Chem. Eur. J. 2011. 17, 11929.
4. B Wang and Z Cao, Angew. Chem. Int. Ed. 2011, 50, 3266.
5. R Wu, Z Lu, Z Cao, and Y Zhang, J. Am. Chem. Soc. 2011, 133, 6110.
6. Y Zhao, N Chen, R Wu, and Z Cao, 2013, submitted.
71
OC11
MECHANISM OF INTRAMOLECULAR HECK REACTION BY DENSITY
FUNCTIONAL THEORY
A. Ayyappan, D. Yogeswara Rao
Indian Institute of Technology Kharagpur, Department of Chemistry, West Bengal 721392 India
Heck Reaction, the palladium-catalyzed C-C coupling between aryl halides or vinyl halides and
activated alkenes in the presence of a base, is widely used in syntheric chemistry. Intramolecular
version of Heck reaction is a route to the generation carbocycles that are scaffolds of many
important natural products and biologically active molecules. Although the mechanism of
intermoelcular Heck reactions is well established, the intramelecular variant is not analyzed in detail
for its mechanistic features. Using Density Functional Theory computations, we have explored the
the catalytic cycle of intramolecular Heck reaction, that involves oxidative addition, migratory
insertion (cyclization) and β-hydride elimination (See Figure). Two pathways were analyzed, which
differ in their initial coordination face (Re or Si) of the terminal alkene with the metal centre. The
choice of pathway is not evident from free energy profile, because one of the pathways have higher
barrier for oxidative addition, the other requires high activation energy for β-hydride elimination.
Detailed analysis of the mechanism will be presented. In addition, our attempts to analyze such
complex reaction mechanisms by kinetic simulations will be discussed.
Figure: Catalytic cycle for the intramolecular Heck reaction.
72
OC12
CYCLODIMERIZATIONS OF DONOR-ACCEPTOR CYCLOPROPANES:
SHORTCUT APPROACH TO COMPLEX RING SYSTEMS
E.M. Budynina, O.A. Ivanova, A.O. Chagarovskiy, I.V. Trushkov
Moscow State University, Department of Chemistry, Moscow, Russia
Cyclodimerization is among the most challenging and fascinating reactions providing significant
increase in structural complexity within one operation step in highly stereoselective manner and
occurring both in vivo and in vitro. In organic synthesis, among typical substrates that undergo
cyclodimerizations, donor-acceptor (DA) cyclopropanes,1 in which small ring is vicinally activated
with donor and acceptor groups, occupy a special place. Currently, at least dozen types of Lewis
acid-triggered cyclodimerization of such DA cyclopropanes as 2-(het)aryl-cyclopropane-1,1diesters are known which open rapid approaches to diverse ring compounds, including complex
polycyclic and bridged molecular systems.2
Recently, on basis of (3+3)-cyclodimerizations of 2-arylcyclopropane-1,1-diesters we developed
straightforward and efficient approaches to 1,4-diarylcyclohexanes, 1-aryltetralins or 9,10dihydroanthracenes.2a (3+2)-Cyclodimerizations of similar cyclopropanes provide an easy access to
diarylcyclopentanes2b,c and arylindanes.2d Cyclodimerizations of 3- and 4-indolyl-derived DA
cyclopropanes allows for the construction of complex tetra- and heptacyclic cores of bisindoles.2e
1. a) Reissig, H.-U.; Zimmer, R. Chem. Rev. 2003, 103, 1151; b) De Simone, F.; Waser, J.
Synthesis 2009, 3353; c) Mel’nikov, M.Ya.; Budynina, E.M.; Ivanova, O.A.; Trushkov, I.V.
Mendeleev Commun. 2011, 21, 293; d) Schneider, T.S.; Kaschel, J.; Werz, D.B. Ang. Chem. Int.
Ed. 2014, 53, 10.1002/anie.201309886.
2. a) Ivanova, O.A.; Budynina, E.M.; Chagarovskiy, A.O.; Trushkov, I.V.; Melnikov, M.Ya. J.
Org. Chem. 2011, 76, 8852; b) Chagarovskiy, A.O.; Ivanova, O.A.; Budynina, E.M.; Trushkov,
I.V.; Melnikov, M.Ya. Tetrahedron Lett. 2011, 52, 4421; c) Novikov, R.A.; Korolev, V.A.;
Timofeev, V.P.; Tomilov, Yu.V. Tetrahedron Lett. 2011, 39, 4996; d) Ivanova, O.A.; Budynina,
E.M.; Skvortsov, D.A.; Limoge, M.; Bakin, A.V.; Chagarovskiy, A.O.; Trushkov, I.V.;
Melnikov, M.Ya. Chem. Commun. 2013, 49, 11482; e) Ivanova, O.A.; Budynina, E.M.;
Chagarovskiy, A.O.; Rakhmankulov, E.R.; Trushkov, I.V.; Semeykin, A.V.; Shimanovskii, N.L.;
Melnikov, M.Ya. Chem. Eur. J. 2011, 17, 11738; f) Novikov, R.A.; Tarasova, A.V.; Korolev,
V.A.; Timofeev, V.P.; Tomilov, Yu.V. Ang. Chem. Int. Ed. 2014, 53, 3187; g) Novikov, R.A.;
Tomilov, Yu.V. Helv. Chim. Acta 2013, 96, 2068.
73
OC13
USING RING STRAIN RELEASE FOR ALLEVIATION OF
TRANSANNULAR STRAIN: SMALL RING-TEMPLATED SYNTHESIS OF
MEDIUM HETEROCYCLES
M. Rubin, M. Rubina, A. Edwards, P. Ryabchuk
University of Kansas, Department of Chemistry
A highly efficient diastereocenvergent reaction of bromocyclopropanes with various nucleophiles
have been recently developed in our laboratories.1-7 This reaction involves a base-assisted
dehydrohalogenation to produce a highly reactive cyclopropene intermediate, which undergoes
subsequent nucleophilic addition across the strained C=C bond. Different intramolecular modes of
this reaction will be presented. Possibilities for assembly of heterocyclic scaffolds with various ring
sizes, including enantiomerically pure medium heterocycles, will be demonstrated. The mechanistic
aspect of this transformation and the means of controlling its diastereoselectivity will be discussed.
O
O
Ph
Me
HN
O
Me
O
N
O
Ph
N
H
t-BuOK/
DMSO
15-membered
t-BuOK/
THF
5-membered
Nu
N
O
KOH/THF
R
Br
O
t-BuOK/THF
18-crown-6 (cat)
Base/THF
O
8-membered
t-BuOK/
DMSO
Ar
Me
H
O
R"'
t-BuOK/
THF
Me
O
7-10-membered
R
O
H
R"
HN
O
O
N
R
R
8-membered
8-9-membered
References
[1] Alnasleh, B. K.; Sherrill, W. M.; Rubina, M.; Banning, J.; Rubin, M. J. Am. Chem. Soc. 2009,
131, 6906-6907.
[2] Banning, J. E.; Prosser, A. R.; Rubin, M. Org. Lett. 2010, 12, 1488-1491.
[3] Prosser, A. R.; Banning, J. E.; Rubina, M. Rubin, M. Org. Lett. 2010, 12, 3968-3971.
[4] Banning, J. E.; Prosser, A. R.; Alnasleh, B. K.; Smarker, J.; Rubina, M.; Rubin, M. J. Org.
Chem. 2011, 76, 3968-3986.
[5] Ryabchuk, P.; Rubina, M.; Xu, J.; Rubin, M. Org. Lett. 2012, 14, 1752-1755.
[6] Banning, J. E.; Gentillon, J.; Ryabchuk, P.; Prosser, A. R.; Rogers, A.; Edwards, A.; Holtzen,
A.; Babkov, I. A.; Rubina, M.; Rubin, M. J. Org. Chem. 2013, 78, 7601-7616.
[7] Ryabchuk, P.; Edwards, A.; Gerasimchuk, N.; Rubina, M.; Rubin, M. Org. Lett. 2013, 15,
6010-6013.
74
OC14
THE STRATEGY FOR ATOM ECONOMICAL REDUCTIVE ADDITION
DEOXYGENATION
D. Chusov, P.N. Kolesnikov, V.I. Maleev, N.Z. Yagafarov
A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences
Herein we present the concept of using carbon monoxide for atom economical reductive addition
deoxygenation without external hydrogen source [1]. We are utilizing this idea by showing that NH and C-H bonds of the reagents could be used as hydrogen source (Fig. 1).
Figure 1
References:
D. Chusov, B. List, Angew. Chem. Int. Ed., 2014, 53, DOI: 10.1002/anie.201400059.
75
OC15
DINUCLEAR CATALYSIS: ACCELERATED, METAL-DEPENDENT RINGOPENING POLYMERIZATION OF LACTIDE
E. Kirillov
Universite de Rennes 1, UMR 6226 - CNRS, 35042 Rennes France
Multinuclear olefin polymerization catalysts (incorporating several active metal centers in one and
the same molecule) have recently emerged as a distinct and brand new class of molecular catalysts. 1
Implicit cooperative behavior2 of two or more metal centers in active species of these systems can
contribute to enhanced performance (with respect to mononuclear analogues) in terms of activity,
chain-transfer kinetics and, also, monomers selectivity in copolymerization reactions.
Dinuclear complexes of aluminum and indium with a bis(phenoxy-imine) platform have been
synthesized and used in the polymerization of lactide.3a Kinetic studies demonstrated that the
dialuminum precursor (Scheme 1) provides a more favorable reaction pathway in terms of
activation free energy than that of directly related monoaluminum systems. 3b No similar trend was
observed with the corresponding diindium / monoindium systems, which was attributed to a
dissimilar ROP mechanism. Details of the mechanisms and key factors of the dinuclear catalysis
will be discussed.
Scheme 1. A dinuclear aluminum system enables a 5-to-10 fold boost in activity when compared to
its monoaluminum analogues.
1. Delferro, M.; Marks, T. J. Chem. Rev. 2011, 111, 2450.
2. Bratko, I.; Gómez, M. Dalton Trans., 2013, 42, 10664.
3. (a) Normand, M.; Roisnel, T.; Carpentier, J.-F.; Kirillov, E. Chem. Commun. 2013, 49, 11692.
(b) Normand, M.; Dorcet, V.; Kirillov, E.; Carpentier, J.-F. Organometallics 2013, 32, 1694.
76
OC16
RECENT METHODOLOGICAL DEVELOPMENTS FOR THE QUANTUM
CHEMICAL STUDY OF COMPLEX SYSTEMS
S. Irle
Nagoya University, Department of Chemistry, Nagoya, Japan
The structural complexity of molecular clusters increases with size due to the associated, rapidly
growing configuration space. Two examples are realized in i) the transition from molecular to bulk
systems, and ii) in the simulation of extended biosystems. In such systems, traditional quantum
chemical approaches of investigations are hampered by the vastly increasing computational cost,
even considering ever-growing supercomputer capabilities. Computationally inexpensive, yet
accurate schemes such as the density-functional tight-binding (DFTB) method [1] and there linear
scaling versions promise here a significant advantage.
We have recently engaged in developing novel methodologies for systems with increasing
structural complexity, driven by motivation from experimental studies. In this presentation, we will
review a) the Kick-fragment-based “Kick3” conformationally aware approach for studying
molecular [2] and ionic liquid clusters with increasing size, and our implementation of the fragment
molecular orbital (FMO) method [3] with DFTB, called “FMO-DFTB”, in the popular GAMESSUS quantum chemistry package [4]. The computational effort of the method scales nearly linearly
with system size with a negligible pre-factor, and allows the efficient, massively-parallel quantum
chemical geometry optimization and direct molecular dynamics (MD) simulations of systems
containing several tens of thousands of atoms, in particular when fragments consist of units with
less than 50 atoms [5]. The method should be particularly useful to predict structures of new
artificial peptides and proteins, predict enzymatic reaction pathways, estimate free energy
contributions along pathways where large parts or even the entire protein including surrounding
water is treated quantum chemically, and to simulate the effects of highly polarizable and/or
charged solvents in explicit-solvent MD simulations.
Unlike other linear scaling schemes, such as divide and conquer approaches (DC), FMO-DFTB's
very design allows the insightful decomposition of interaction energies between ligands and
proteins in terms of electrostatics, exchange-repulsion, charge transfer, dispersion and solvent
screening contributions in a straightforward manner.
[1]
[2]
[3]
[4]
M. Gaus, Q. Cui, M. Elstner, J. Chem. Theory Comput. 7, 931 (2011).
M. A. Addicoat, S. Fukuoka, A. J. Page, S. Irle, J. Comput. Chem. 34, 2591 (2013).
D. G. Fedorov, T. Nagata, K. Kitaura, Phys. Chem. Chem. Phys. 14, 7562 (2012).
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S.
Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis and J. A. Montgomery,
Jr., J. Comput. Chem., 1993, 14, 1347; http://www.msg.ameslab.gov/gamess/index.html.
[5] Y. Nishimoto, D. G. Fedorov, S. Irle, submitted.
77
OC17
QUANTUM CHEMICAL MODELING IN STUDIES OF MOLECULAR
MECHANISMS OF ENZYME CATALYSIS
A.V. Nemukhin
Chemistry Department, M.V. Lomonosov Moscow State University, Moscow, 199991, Russia; N.M.
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia
Recent results [1-3] of modeling chemical transformations in enzyme active sites using quantumbased approaches will be discussed. We apply quantum mechanics/molecular mechanics (QM/MM)
approaches to compute minimum energy pathways connecting enzyme-substrate and enzymeproduct complexes. Appropriate crystal structures from the Protein Data Bank usually serve as a
source of coordinates of heavy atoms to create molecular model systems. After in silico
construction of a three-dimensional full-atom model, evolution of the model system along carefully
selected reaction coordinates is analyzed.
Several examples of such modeling will be presented. The complete cycle of chemical
transformations in penicillin acylase, a unique enzyme that belongs to the recently discovered
superfamily of N-terminal nucleophile hydrolases, with its most specific substrate, penicillin G,
leading to formation of 6-aminopenicillanic and phenylacetic acids [1] will be presented. Ketonketal transformations at the active site of matrix metalloproteinases characterized computationally
[2] may be explored to propose specific inhibitors. Chemical reactions in photoreceptor proteins
constitute an active field of application of QM/MM modeling; the case of BLUF domains will be
discussed [3].
Simulation results of guanosine triphposphate hydrolysis (GTP) by small GTPases, icluding Ras
protein, will be in focus. According to newly obtained data, the molecular events of the chemical
steps upon GTP hydrolysis include: (i) cleavage of the phosphorus (Pγ) -oxygen bond in GTP upon
approach of the properly aligned catalytic water molecule, producing GDP; (ii) formation of a new
chemical bond between phosphorus and oxygen of water; (iii) redistribution of protons between
reacting species leading to inorganic phosphate Pi.
References
[1] Grigorenko B.L., Khrenova M.G., Nilov D.K., Nemukhin A.V., Švedas V.K. Catalytic Cycle of
Penicillin Acylase from Escherichia coli: QM/MM Modeling of Chemical Transformations in
the Enzyme Active Site upon Penicillin G Hydrolysis // ACS Catal. 2014. V. 4. P. 2521–2529.
[2] Khrenova M.G., Nemukhin A.V., Savitsky A.P. Computational Characterization of KetoneKetal Transformations at the Active Site of Matrix Metalloproteinases // J. Phys. Chem. B. 2014.
V. 118. P. 4345-4350.
[3] Khrenova M.G., Nemukhin A.V., Domratcheva T. Photoinduced Electron Transfer Facilitates
Tautomerization of the Conserved Signaling Glutamine Side Chain in BLUF Protein Light
Sensors // J. Phys. Chem. B. 2013 V. 117. P. 2369-2377.
78
OC18
EXCITED STATES AND MOLECULAR INTERACTIONS IN PROTEINS
AND SOLUTIONS
J.H. Hasegawa
Catalysis Research Center, Hokkaido University, Sapporo, Japan
Solvatochromism and fluorescent solvatochromism are well-known phenomena, and there are rich
accumulations in experimental publications. Color tuning in proteins, such as human color vision
and fluorescent proteins, could be also classified to solvatochromism but with a specific
environment where anisotropic molecular interactions play important roles.
We have studied biological color tuning with the SAC-CI/MM calculations in which MM
description was adopted for the environmental effect. This classical description for the environment
works very well for explaining the color tuning mechanisms.
In some cases, however, environmental electronic structure effect becomes important. To
investigate the origin of the QM effect, we propose a scheme based on the wave function theory
with a MO localization scheme. The role of the environmental electronic effect was analyzed in
terms of amino acids’ orbital delocalizations, excitonic interactions, excited-state polarization, and
dispersion interactions. In the presentation, we would show some results of pilot applications.
79
OC19
CATIONIC GOLD-CATALYZED HETEROANNULATIONS
E.V. Van Der Eycken
University of Leuven (KU Leuven), Department of Chemistry, Leuven, Belgium
Gold catalysis is one of the fast growing research topics of modern organic chemistry. In this
context, gold-catalyzed carbocyclization and heteroannulation strategies have recently attracted
much attention due to the selective and efficient activation of the C-C triple bond towards a wide
range of nucleophiles. Moreover, the combination of multicomponent reactions with gold catalysis,
gives access to complex molecular architectures in few steps, as compared to traditional multistep
processes. We will comment on our recent findings in this field. A concise route to indoloazocines1
via a sequential Ugi/gold-catalyzed intramolecular hydroarylation2 will be presented. A diversityoriented approach to spiroindoles via a post-Ugi gold-catalyzed diastereoselective domino
cyclization3 will be described (Scheme), as well as a regioselective approach for the synthesis of
pyrrolopyridinones and pyrroloazepinones employing a gold(I)/platinum(II) switch.4
O
H2N
R1
+
N
R2
O
R3
N
R4
NC
5
R
R3
i) Ugi-4CR
ii) "cationic gold", rt
COOH
O
R
1
N
H
R2
N
R5
(+/-)
R
4
13 examples
up to 80% yield
References:
1. Synthesis of Azocino[5,4-b]indoles via Au-Catalyzed Intramolecular Alkyne Hydroarylation, V.
A. Peshkov, O. P. Pereshivko, E. V. Van der Eycken, Adv. Synth. Cat., 354, 2841-2848, 2012.
2. Concise route to indoloazocines via a sequential Ugi/gold-catalyzed intramolecular
hydroarylation, S. G. Modha, D. D. Vachhani, J. Jacobs, L. Van Meervelt, E. V. Van der
Eycken, Chem. Commun., 48 (52), 6550–6552, 2012.
3. Diversity-Oriented Approach to Spiroindolines: Post-Ugi Gold-Catalyzed Diastereoselective
Domino Cyclization, S. G. Modha, A. Kumar, D. D. Vachhani, J. Jacobs, S. K. Sharma, V. S.
Parmar, L. Van Meervelt, E. V. Van der Eycken, Angew. Chem. Int. Ed., 51, 9572-9575, 2012.
4. Gold(I) and Platinum(II) switch: A post-Ugi intramolecular hydroarylation to pyrrolopyridinones
and pyrroloazepinones, S. G. Modha, A. Kumar, D. D. Vachhani, S. K. Sharma, V. S. Parmar, E.
V. Van der Eycken, Chem. Comm., 48, 10916-10918, 2012.
80
OC20
Pd-SUPPORTED BIMETALLIC COMPOSITIONS FOR
STEREOSELECTIVE LIQUID PHASE SEMI-HYDROGENATION OF
DIPHENYLACETYLENE
I.S. Mashkovsky1, A.V. Sergeeva1, O.V. Turova1, M.N. Vargaftik2, N.Yu. Kozitsyna2, A.Yu.
Stakheev1
1 - Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia
2 - Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russia
This study was focused on the development of the efficient catalyst for selective semihydrogenation of internal alkene. Diphenylacetylene (DPA) was used as a model compound. The
catalytic compositions based on Pd-Zn, Pd-Co, Pd-Ni were investigated. The samples were
prepared via two techniques: (1) on the basis of palladium acetate heterobimetallic complexes as
precursors and (2) using traditional co-impregnation by individual metal salts. It was found that the
systems based on bimetallic acetate complexes exhibited a substantial increase in selectivity to
alkene and cis-isomer formation at high conversion of the parent alkyne (DPA), albeit at the
expense of some decrease in the activity. The detailed physicochemical study with TEM-EDS,
SEM-EDS, EXAFS and IR-spectroscopy reveals that the use of heterobimetallic acetate complex as
a precursor allows us to avoid metallic phase segregation during the reduction treatment of the
catalyst, which ensures high homogeneity of bimetallic particles and leads to enhanced selectivity.
Financial support was provided by RFBR foundation, grants #12-03-31487, 13-03-12176
0.93%Pd-0.53%Co/Al2O3
100
90
0.93%Pd-0.53%Co/Al2O3
90
Selectivity to alkene, %
Selectivity to cis-isomer, %
100
80
70
0.93%Pd-0.53%Ni/Al2O3
60
0.93%Pd-0.52%Zn/Al2O3
50
40
H
30
0.93%Pd/Al2O3
H
80
0.93%Pd-0.53%Ni/Al2O3
70
0.93%Pd-0.52%Zn/Al2O3
60
50
0.93%Pd/Al2O3
40
H
30
20
20
10
10
H
H
+
H
0
0
70
80
90
100
70
80
90
100
DPA conversion, %
DPA conversion, %
Рис. 1 Dependency of selectivity to cis-isomer and alkene on DPA conversion for Pd/Al2O3
catalyst modified with Co, Zn and Ni in liquid phase DPA hydrogenation.
81
OC21
DESIGN OF NANOSTRUCTURES ON THE BASIS OF TWO
PHARMACOPHORIC FRAGMENTS - FULLERENE AND PIPERIDINE
DERIVATIVES
G.V. Grishina, I.S. Veselov, I.V. Trushkov
M. V. Lomonosov Moscow State University, Department of Chemistry
This communication is described the creation of a new nanobiosystems with high antivirus potential
based on the two pharmacophoric fragments - derivatives of fullerene C60 and piperidine ligands.
Design of nanoadditive on the basis of two pharmacophoric fragments - functional derivatives of
trans-3,4-dihydroxypiperidine and organically modified by fullerene C60 can be a very promising
bioactive substances. Such a perspective is related to using, first, as ligands several trans-3,4dihydroxylated piperidines already demonstrated anti-HIV activity, and secondly, the uniqueness of
fullerene spheroid significantly reduce the toxicity of biologically active adducts. We believed that
binding of two biologically active units in the same system will be very useful and promising.
Y
M
e
N
Y
N
X
N
O
X
C
O
O
E
t
1
: X
=H
,Y
=O
H
2
: X
=Y
=O
H
3
:X
=
N
H
R
,Y
=O
H
4
Monoadducts 1-4 have obtained by the Benguel and Prato reactions, respectively, and have since
received 12 new fullerene adducts based on the derivatives of the trans-3,4-dihydroxypyridine and
trans-4-amino-3-hydroxypiperidines. Isolation, and identification of these adducts were made using
column and preparative chromatography on silica gel, structure and stereochemistry were
established with the involvement required in each case, spectral methods, including mass
spectrometry and МАLDI, X-ray analysis and 1H, 13C NMR. The main difficulty in undertake
researches consisted of significant differences reactivity due to high lipophilicity derivatives of
fullerene and high hydrophilicity piperidine ligands. To reduce this difference, we have modified
both fragments introduction to piperidine ligands and/or in the molecule organically modified
fullerenes functions and/or linkers, which facilitated further obtaining of target adducts. For some
samples of adducts managed to get soluble in alcohol salts. A very important factor has been the
elucidation of the impact of structural and stereochemical factors on possible synergies in the
adduct investigation. Target adducts are a new type of nanostructures for medical chemistry with
great pharmacological potential.
82
OC22
CHIRASAC STUDY ON CHIRAL SPECTROSCOPY AND PHOTOBIOLOGY
H. Nakatsuji, T. Miyahara
Quantum Chemistry Research Institute (QCRI), 1-36 Goryo-Oohara, Nishikyo-ku, Kyoto 615-8245,
Japan
Weak interactions of molecules with solvents and/or environments are of crucial importance in
material science and biology, but rather difficult to investigate quantitatively. Circular dichroism
(CD) spectra reflect sensitively the conformational structures of chiral molecules, their (weak)
interactions with solvents and/or proteins, etc. The SAC-CI method gives their CD spectra very
reliably. From this fact, the SAC-CI method is a useful tool to investigate the conformational
geometries of chiral molecules, their interactions with environments, etc by comparing their
experimental and SAC-CI theoretical CD spectra. We initiated a systematic molecular technology,
called ChiraSac (Chirality + SAC-CI) project (see Figure 1) by using the SAC-CI code and other
highly reliable and useful codes on “GAUSSIAN” suit of programs [1]. We have already applied
this project successfully to several topics of chiral spectroscopy and photobiology [2-4]. We will
present here conformational dependence of α-Hydroxyphenylacetic Acid and similarities and
differences between RNA and DNA, etc, as some recent applications of ChiraSac to chiral
spectroscopy and photobiology.
References:
[1] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G.
E. Scuseria, M. A. Robb, J. R. Cheeseman, G.
Scalmani, V. Barone, B Mennucci,. G. A.
Petersson, et al., Gaussian 09, Gaussian, Inc.,
Wallingford, CT, 2009.
[2] Circular Dichroism Spectra of Uridine
Derivatives:
ChiraSac
Study,
Tomoo
Miyahara, Hiroshi Nakatsuji, and Takehiko
Wada, J. Phys. Chem. A 118, 2931-2941
(2014).
[3] Conformational Dependence of the Circular
Dichroism Spectrum of α-Hydroxyphenylacetic Acid: A ChiraSac Study, Tomoo
Miyahara and Hiroshi Nakatsuji, J. Phys.
Chem. A 117, 14065- 14074 (2013).
[4] Helical Structure and Circular Dichroism
Spectra of DNA: A Theoretical Study, T.
Miyahara, H. Nakatsuji, and H. Sugiyama, J.
Phys. Chem. A. 117, 42-55 (2013).
83
OC23
A DFT ANALYSIS ON THE ELECTRONIC PROPERTIES OF
METHYLAMMONIUM LEAD IODIDE PEROVSKITE
K. Yamashita1, G. Giorgi1, J. Fujisawa2, H. Segawa2
1 - Department of Chemical System Engineering, The University of Tokyo, Japan
2 - Research Center for Advanced Science and Technology, The University of Tokyo,Japan
Methylammonium (MA) lead iodide perovskite (CH3NH3PbI3) plays an important role in light
absorption and carrier transport in efficient organic−inorganic perovskite solar cells [1]. In my talk,
the first theoretical estimation of effective masses of photocarriers and the role of MA cation in
CH3NH3PbI3 will be discussed.
Spin-polarized DFT calculations have been performed with the generalized gradient approximation.
From the charge density of the two-fold degenerate states ((a) and (b)) of CBM and those ((c) and
(d)) of VBM, one can see that photogenerated electrons around CBM and holes around VBM exist
separately, results related to the ambipolar transport nature of the material. Effective masses of
photogenerated electrons and holes are estimated to be me* =0.23m0 and mh* = 0.29m0,
respectively, including spin−orbit coupling (SOC) effects. This result is consistent with the longrange ambipolar transport property and with the larger diffusion constant for electrons compared
with that for holes in the perovskite, which enable efficient photovoltaic conversion [2].
We also have focused our attention on the MA cation and studied the role it plays in the
electronic/optical features of the perovskite, paying attention mainly to the iodide compound [3]. A
comparison is performed between the electronic properties of MAPbI3 organic-inorganic perovskite
and those of the purely inorganic CsPbI3.
References
1. J. Bisquert, J. Phys. Chem. Lett, 4, 2597 (2013).
2. G. Giorgi, J. Fujisawa, H. Segawa, K. Yamashita, J. Phys. Chem. Lett, 4, 4213 (2013).
3. G. Giorgi, J. Fujisawa, H. Segawa, K. Yamashita, J. Phys. Chem. 118, 12176 (2014).
84
OC24
A HYBRID MC/MD REACTION METHOD WITH RARE EVENT-DRIVING
MECHANISM: ATOMISTIC REALIZATION OF 2-CHLOROBUTANE
RACEMIZATION PROCESS IN DMS SOLUTION
M. Nagaoka
Graduate School of Information Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 4648601, Japan; Core Research for Evolutional Science and Technology (CREST), Japan Science and
Technology Agency (JST), Honmachi, Kawaguchi 332-0012, Japan; ESICB, Kyoto University,
Kyodai Katsura, Nishikyo-ku, Kyoto 615-8520, Japan
We demonstrate a new efficient hybrid MC/MD reaction method with a rare event-driving
mechanism as a practical ‘atomistic’ molecular simulation of large-scale chemically reactive
systems (Figure 1). Application of the method to (R)-2-chlorobutane molecules in N,Ndimethylformamide (DMF) molecules starting in the optical pure state (100% e.e.) was found to
successfully provide such an atomistic state with ~0% e.e., the expected purity of (R)- to (S)enantiomers of the racemic mixture in chemical equilibrium [1].
This hybrid MC/MD reaction method is promising for studies of various properties in chemically
reactive systems [2] and their stereochemistry as well.
Figure 1. Schematic representation of the hybrid MC/MD reaction method. The curly curves
represent the molecular dynamical (MD) moves in phase space following the equations of motion,
while the straight lines with arrows represent the Monte Carlo (MC) moves (or transitions) of the
system (right figure), whose dynamical moves would be extremely rare events. In the left figure, the
configurational distribution in equilibrium peq is proportional to the exponential factor exp[-βU]
where U is the global potential function. The right figure shows regional distributions, e.g., preq
exp[-βUr] in region r, etc. The connecting points of the two kinds of moves (open circles) are
selected according to the criteria for chemical reaction occurrence. Note that they do not represent
real connections since these points correspond to almost identical states in configuration space but
not in momentum space and with different configurational gradients. Wr→s and Ws→t are the
transition probabilities from state r to s and from s to t, respectively [1].
[1] Masataka Nagaoka, Yuichi Suzuki, Takuya Okamoto, Norio Takenaka, Chem. Phys. Lett. 583,
80 (2013).
[2] N. Takenaka, Y. Suzuki, H. Sakai, M. Nagaoka. J. Phys. Chem. C, 118, 10874 (2014).
85
OC25
CALIX[4]ARENE-TETRATHIAFULVALENE RECEPTORS FOR
RECOGNITION OF ELECTRON DEFICIENT GUESTS
V.A. Azov, M.H. Duker, H. Schafer, D. Schluter
University of Bremen
For more than four decades tetrathiafulvalenes1 (TTFs) have been extensively studied on the
account of their outstanding –donating properties. Due to their ability to induce reversible
electrochemically-switchable processes,1b TTFs have found their place on the forefront of
supramolecular chemistry. Herein, we present synthesis and studies of a family of rationally
designed redox-switchable receptors employing monopyrrolo-tetrathiafulvalenes as molecular
recognition units.
Our group has been long interested in synthesis and studies of tetrathiafulvalene-containing
molecular architectures and their application for binding of electron-deficient molecular guests.2
Recently, several upper rim bis-monopyrrolotetrathiafulvalene-calix[4]arene receptors were
synthesized using a modular construction approach.3a,b These compounds feature an architecture of
molecular tweezers:4 two parallel aligned electron rich TTF arms comprise a molecular recognition
center.
Addition of planar electron-deficient guests, such as tetracyanoquinodimethane (TCNQ), to a
receptor solution leads to formation of deeply-colored charge-transfer complexes, easily visible by a
naked eye. Binding titrations were performed to determine the binding constants, which reached as
high as 1 104 M-1. Additionally, tripodal receptors comprising three TTF units attached to the
1,3,5-substituted-2,4,6-triethylbenzene scaffold, showed high affinity to pyridinium derivatives in
the gas phase, as it was proven by ESI-MS experiments.3c
1. a) J. L. Segura, N. Martín, Angew. Chem. Int. Ed. 2001, 40, 1372–1409; b) D. Canevet, M. Sallé,
G. Zhang, D. Zhang, D. Zhu, Chem. Commun. 2009, 2245–2269.
2. a) V. A. Azov, R. Gómez, J. Stelten, Tetrahedron 2008, 64, 1909–1917; b) M. Skibiński, R.
Gómez, E. Lork, V. A. Azov, Tetrahedron 2009, 65, 10348–10354; c) M. H. Düker, R. Gómez,
C. M. L. Vande Velde, V. A. Azov, Tetrahedron Lett. 2011, 52, 2881–2884.
3. a) M. H. Düker, H. Schäfer, M. Zeller, V. A. Azov, J. Org. Chem. 2013, 78, 4905–4912; b) V.
A. Azov, H. Schäfer, D. Schlüter, manuscript in preparation; c) M.-L. Lieunang Watat, T.
Dülcks, D. Kemken, V. A. Azov, Tetrahedron Lett. 2014, 55, 741–744.
4. For a review on topologically similar molecular tweezers, see: F.-G. Klärner, B. Kahlert, Acc.
Chem. Res. 2003, 36, 919–932.
86
OC26
ENHANCED RATE AND SELECTIVITY BY CARBOXYLATE SALT AS A
BASIC COCATALYST IN CHIRAL NHC-CATALYZED ASYMMETRIC
ACYLATION OF SECONDARY ALCOHOLS
K. Yamada
Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 6068501, Japan
Kinetic resolution of racemic secondary alcohols via enantioselective acylation is an important
process in synthetic chemistry.1 During a study to extend our previous report,2 we found that the
rates and enantioselectivities of chiral NHC-catalyzed asymmetric acylation of alcohols with an
adjacent H-bond donor functionality are remarkably enhanced in the presence of a carboxylate
cocatalyst. The degree of the enhancement is correlated with the basicity of the utilized carboxylate.
Using a cocatalyst and newly developed electron-deficient chiral NHC, kinetic resolution and
desymmetrization of cyclic diols and amino alcohols are achieved with extremely high selectivity
(up to krel = 218 and 99% ee, respectively) with low catalyst loading (0.5 mol %).3
References
1 Müller, C. E.; Schreiner, P. R. Angew. Chem. Int. Ed. 2011, 50, 6012.
2 Kuwano, S.; Harada, S.; Oriez, R.; Yamada, K. Chem. Commun. 2012, 48, 145.
3 Kuwano, S.; Harada, S.; Kang, B.; Oriez, R.; Yamaoka, Y.; Takasu, K.; Yamada, K.
J. Am. Chem. Soc. 2013, 135, 11485.
87
OC27
CONFORMATIONAL FLEXIBILITY, INTRA- AND INTERMOLECULAR
INTERACTIONS AND CATALYTIC ACTIVITY OF PC(sp3)P PINCER
IRIDIUM HYDRIDE COMPLEXES
N.V. Belkova1, G.A. Silantyev1, O.A. Filippov1, S. Musa2, D. Gelman2, L.M. Epstein1, E.S.
Shubina1
1 - A.N. Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia
2 - The Hebrew University of Jerusalem, Jerusalem, Israel
A variety of recently developed catalysts operate via different ligand-metal cooperating
mechanisms and new “non-innocent” ligands and their complexes keep appearing in the literature.
Reversible switching between different coordination modes found in these compounds opened new
practical reactivity patterns in non-oxidative (i.e. alternative to the conventional oxidative
addition/reductive elimination sequence) activation and formation of polar and non-polar bonds. At
that, many such systems contain stereochemically rigid pincer ligands and keep their geometry
during the catalytic runs.
Bifunctional dibenzobarrelene-based PC(sp3)P pincer iridium complex 1 is known as an efficient
catalyst in acceptorless dehydrogenation of alcohols [1] and hydrogenation/hydroformylation of
alkenes [2]. In order to shed light on the mechanism of the hydrogen formation/activation, we
performed variable temperature IR and NMR (1H, 31P) analysis of intra- and intermolecular
interactions involving hydride ligand and hydroxymethyl cooperating group in 1 and its analogues.
The results of the spectroscopic measurements in different media (dichloromethane, toluene,
DMSO, and mixed solvents) were compared with the quantum chemical (DFT /M06 and B3PW91;
AIM) calculations. The data obtained imply flexibility of the dibenzobarrelene-based scaffold
unprecedented for conventional pincer ligands. Both the complex 1 and its counterpart 2 prefer
facial configuration of the PCP ligand with P-Ir-P angle of ca. 100º. Such geometries are dictated by
stabilizing Ir···O interaction and differ by the mutual arrangement of the H and Cl ligands. The
complexes show dynamic equilibrium between two most stable fac-isomers, which can be
transformed into the meridional ones in the presence of coordinating additives (CH3CN, DMSO or
CO, but not Et3N), some of which have been used as auxiliary base in catalytic alcohols
dehydrogenation [1]. The mechanism of the H2 activation and C-H bond formation involves
intramolecular cooperation between the structurally remote CH2OH functionality and the metal
center and proceeds without the change of the oxidation state of the metal.
This work was financially supported by the Russian Foundation for Basic Research (projects No.
14-03-00594 and 14-03-31828) and by the German-Russian Interdisciplinary Science Center (GRISC) funded by the German Federal Foreign Office via the German Academic Exchange Service
(DAAD) (projects No. C-2011b-4 and C-2012a-4).
1. S. Musa, I. Shaposhnikov, S. Cohen, D. Gelman, Angew. Chem. Int. Ed. 2011, 50, 3533-3537
2. Musa, S.; Filippov, O. A.; Belkova, N. V.; Shubina, E. S.; Silantyev, G. A.; Ackermann, L.; Gelman, D.
Chem. Eur. J. 2013, 19, 16906-16909
88
OC28
RECENT DEVELOPMENT OF THE FRAGMENT MOLECULOR ORBITAL
METHOD
K. Kitaura
Department of Computational Science, Graduate School of System Informatics, Kobe University ,
Chuo-ku, Kobe, 650-0047, Japan
The fragment molecular orbital (FMO) method[1] is an approximate ab initio MO computational
method for vary large molecules such as proteins. In the method a molecule is divided into
fragments and ab initio MO calculations are performed on the fragments, their dimers and
optionally trimers to obtain the total enegy and other properties of the whole molecule. The method
reproduces regular ab initio properties with good accuracy. Various FMO-based correlation
methods have been developed including density functional theory (DFT), 2nd order Møller-Plesset
perturbation theory (MP2), coupled cluster theory (CC), and MCSCF. Polarisable continuum model
(PCM) was interfaced with FMO, allowing one to treat solvent effects of real size proteins. The
FMO codes been incorporated in GAMESS-US[2].
Recently, We have developed the analytical energy gradients [3] and the second derivatives[4] in
FMO. In this presentation, I will talk about the applications to geometry optimization, MD
simulation, and vibrational frequency calculations of large molecular systems.
[1] “The faragment Molecular Orbital Method: Practical Applications to Large Molecular Systems”,
Dmitri.G..Fedorov, Kazuo Kitaura, Eds., CRC press, Boca Raton, 2009.
[2] GAMESS, http://www.msg.ameslab.gov/gamess/
[3] T. Nagata, et al., J. Chem. Phys. 135, 044110 (2011)
[4] H. Nakata, et al., J. Chem. Phys. 138, 164103 (2013)
89
OC29
MODELING ADSORPTION IN NANOSCALE DEFECTIVE Pd2-GRAPHENE
SYSTEMS
M.V. Polynski, V.P. Ananikov
ZIOC RAS, Leninsky prospekt, 47, 119991 Moscow, Russia; MSU, Faculty of Chemistry, 1-3
Leninskiye Gory, 119991 Moscow, GSP-1, Russia
Quantum chemical modeling of transition metal particle adsorption on defeted graphene is still
challenging due to the fact that periodic systems of tens or even hundreds of atoms have to be
considered. We use DFT methods to evaluate Pd2 affinity to defect sites on graphene surface.
GPW method [1] implemented in CP2k program [2] (version 2.6, development) was used for all the
computations presented. Spin-polarized computations with dispersion-corrected PBE-D3 functional
were performed in all cases unless specified explicitly. GTH-type pseudopotentials for PBE
functional and DZVP-MOLOPT-SR-GTH basis set were used. The model systems were treated as
2D-periodic unless specified explicitly. The geometry optimizations were performed with the BFGS
algorithm. Cell parameters were kept fixed during geometry optimizations.
Pd2 molecules were placed near a defect in several spatial configurations and this model systems
were subjected to geometry optimization. The affinity of Pd2 species to various point- and 1Ddefects, and steppings was evaluated, and both magnetic and non-magnetic states were found. The
PBE-D3 method allowed to model a system with both covalent and non-covalent interactions.
Noteworthy, the model systems are truly nanoscale (the cell vectors are longer than ~2 nm) and
contain up to ~430 atoms.
Optimized structures of Pd2 binded to double vacancy defect site (left)
and Stone-Wales-type defect site (right).
The reported study was supported by the Supercomputing Center of Lomonosov Moscow State
University [3].
[1] VandeVondele, J.; Krack, M.; Mohamed, F.; Parrinello, M.; Chassaing, T.; Hutter, J. Comp.
Phys. Commun. 2005, 167, 103.
[2] Hutter, J.; Iannuzzi, M.; Schiffmann, F.; VandeVondele, J. Wiley Interdisciplinary Reviews:
Computational Molecular Science 2014, 4, 15.
[3] Sadovnichy, V.; Tikhonravov, A.; Voevodin, Vl.; Opanasenko, V. "Lomonosov":
Supercomputing at Moscow State University. In Contemporary High Performance Computing:
From Petascale toward Exascale; Vetter, J. S., Ed.; Chapman & Hall/CRC Computational
Science, CRC Press: Boca Raton, USA, 2013; pp 283-307.
90
OC30
CLUSTER EFFECT IN DECHLORINATION OF ORGANOCHLORIDES BY
BIMETALLIC Au-Ag SYSTEM: EXPERIMENTAL AND THEORETICAL
STUDY
L.V. Romashov, L.L. Khemchyan, E.G. Gordeev, V.P. Ananikov
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prosp. 47,
Moscow 119991, Russia
Environmental pollution by various chlorinated organic compounds is the problem of great
importance nowadays. Various aliphatic and aromatic chlorides have found applications as solvents,
dry cleaning fluids, degreasing agents, pesticides, insecticides etc. and have been produced in large
quantities during the last decades. Extensive use and chemical stability of chlorinated compounds
led to widespread contamination of environment by these pollutants.[1]
In recent decades interesting results were achieved using bimetallic systems as promoters of
dechlorination process. Interaction between different metal atoms results in superior properties,
which significantly exceed a simple combination of individual metals.[2-5] In spite of very
promising potential, the origin of bimetallic effect remains unclear and mechanistic picture of
bimetallic dechlorination is an open question.
Experimental study of dechlorinative activity of Au/Ag bimetallic system has shown formation of a
variety of chlorinated bimetallic Au/Ag clusters with well-defined Au:Ag ratio from 1:1 to 4:1
(Figure 1). It is the formation of the Au/Ag cluster species that mediated C-Cl bond breakage, since
neither Au nor Ag species alone exhibited a comparable activity (Figure 2). The nature of the
products and the mechanism of dechlorination were investigated by ESI-MS, GC-MS, NMR and by
quantum chemical calculations at the M06/6-311G(d)&SDD level of theory. It was revealed that
formation of bimetallic clusters facilitated dechlorination activity due to thermodynamic factor.
An appropriate Au:Ag ratio for efficient hydrodechlorination process was determined in a joint
experimental and theoretical study carried out in the present work. High activity of the designed
bimetallic system made it possible to carry out dechlorination process under mild conditions at
room temperature.
Figure 1. Example of detected bimetallic
Figure 2. Bimetallic effect in dechlorination
cluster (optimized geometry).
reaction.
[1] Thornton, J., Pandora's Poison: Chlorine, Health, and a New Environmental Strategy. MIT
Press: MA, 2000.
[2] Nutt, M. O.; Hughes, J. B.; Wong, M. S. Environ. Sci. Technol. 2005, 39, 1346-1353.
[3] De Corte, S.; Sabbe, T.; Hennebel, T.; Vanhaecke, L.; De Gusseme, B.; Verstraete, W.; Boon,
N. Water Res. 2012, 46, 2718-2726.
[4] De Corte, S.; Hennebel, T.; Fitts, J. P.; Sabbe, T.; Biznuk, V.; Verschuere, S.; van der Lelie, D.;
Verstraete, W.; Boon, N. Environ. Sci. Technol. 2011, 45, 8506-8513.
[5] Lambert, S.; Ferauche, F.; Brasseur, A.; Pirard, J. P.; Heinrichs, B. Catal. Today 2005, 100, 283289.
91
OC31
PORPHYRIN-FULLERENE DYADS COVALENTLY LINKED VIA
PYRROLO[3,4-C]PYRROLE LINKER: ON THE WAY TO MOLECULES
FORMING LONG-LIVED CHARGE-SEPARATED STATE
A.S. Konev, P.I. Prolubnikov, A.F. Khlebnikov, A.S. Mereshchenko, A.V. Povolotskiy, O.V. Levin
St. Petersburg State University, Institute of Chemistry, St. Petersburg, Russian Federation
Porphyrinofullerenes represent promising materials for artificial photosynthesis and for construction
of organic photovoltaic devices1 due to their ability to form charge-separated state (CS) upon
irradiation with light. The lifetime of the CS thus formed ranges from pico-2 to microsecond3 range,
depending on the structure of the dyad and on the conditions of irradiation. The larger the lifetime
of the CS, the higher is the probability of worthwhile intermolecular electron transfer from a
photochemically generated radical-ion pair, making thus a creation of the systems that are capable
to form a long-lived CS an important task.
Analysis of the relevant literature shows that a porphyrin-fullerene dyad with rigid linker that
enables spatial separation of the chromophors and fixes them in face-to-edge orientation, so that
their π-systems are virtually orthogonal one to another, should reduce the rate of back-electron
transfer and enhance thus the lifetime of the CS. Keeping in mind this strategy of achieving longlived CS species, we synthesized a series of covalently linked porphyrin-fullerene dyads with a
rigid pyrrolo[3,4-c]pyrrolic linker that meets the above requirements and studied them by means of
transient absorption spectroscopy and cyclic voltammetry. The lifetime of the charge separated state
constituted up to 4 μs, depending on the substituents in the porphyrin core. The effect of the
porphyrin substituent on the lifetime of the CS was rationalized on the basis of DFT and TD-DFT
B3LYP(6-31G(d)) calculations of ground and excited electronic states of model compounds.
Ar
CO2Et
O
EtO2C
532 nm
N
Ar
N
N
N
NH
HN
N
CO2Et
O
EtO2C
F
P
up to 4 μs
Ar
CO2Et
O
NH2
N
H
N
N
CO2Et
H2N
Ar-CHO
O
N
O
O
References
1. D. M. Guldi, Chem. Soc. Rev., 2002, 31, 22
2. e.g.: N.V. Tkachenko, H. Lemmetyinen, J. Sonoda, K. Ohkubo, T. Sato, H. Imahori, Sh.
Fukuzumi, J. Phys. Chem. A, 2003, 107, 8834
3. e.g.: M.E. El-Khouly, K.-J. Han, K.-Y. Kay, Sh. Fukuzumi, Eur. J. Chem. Phys. Phys. Chem.,
2010, 11, 1726.
The work was financially supported by the Russian Foundation for Basic Research (Grant No. 1403-00187), St. Petersburg State University (Grants No. 12.38.78.2012, 12.50.1562.2013) and St.
Petersburg State University/DAAD joint program (A1178335/12.23.508.2012).
92
OC32
PALLADIUM-CATALYZED CASCADE ANNULATION OF ALKYNES
WITH UNACTIVATED ALKENES IN IONIC LIQUIDS
J.-X. Li, S.-R. Yang, H.-F. Jiang
South China University of Technology, School of Chemistry and Chemical Engineering,
Guangzhou, P. R. China
Transition metal-catalyzed carbon-carbon or/and carbon-heteroatom bond formations have attracted
considerable attention over the past decades, owing to their easy access to highly functionalized
molecules in an efficient, atom- and step-economical way.[1] Particularly, palladium-catalyzed
cascade reactions have been emerging as a captivating branch of organic chemistry, associating
with the mild reaction conditions and excellent functional group tolerance in a fashion of green
chemistry.[2] On the other hand, ionic liquids offer an alternative and ecologically sound medium in
comparison to conventional organic solvents, as they are nonvolatile, recyclable, highly compatible
with transition metal catalysts, limited miscibility with common solvents enables easy product and
catalyst separation with the retention of catalyst activity in the ionic phase.[3]
Recently, we have investigated various palladium(II)-catalyzed cascade transformations of alkynes
and alkenes in ionic liquids (Scheme 1, Path I-III). As part of our research programs in
nucleopalladation and Pd-catalyzed cross-coupling reactions in ionic liquids, we herein present the
first example of palladium-catalyzed intermolecular cascade annulation of alkynes with unactivated
alkenes in ionic liquids to afford a series of functionalized alkene products (Scheme 1, Path IV).
Scheme 1
Reference:
[1] Gulevich, A. V.; Dudnik, A. S.; Chernyak, N.; Gevorgyan,V. Chem. Rev. 2013, 113, 3084.
[2] Wu, W.; Jiang, H. Acc. Chem. Res. 2012, 45, 1736.
[3] Giernoth, R. Angew. Chem., Int. Ed. 2010, 49, 2834.
93
OC33
SYNTHESIS OF BENZOTHIADIAZOLE COMPOUNDS FOR OPTICAL
MATERIALS
Y.L. Li, S.H. Chen
Institute of Chemistry, Chinese Academy of Sciences,CAS Key Laboratory of Organic Solids,
Beijing, P.R. China
The nature of the substituent groups greatly influences the structural and photophysical properties
of D/A molecules. The nature of the linkage between the D and A units also influences the
structures and photophysical properties of intramolecular charge transfer (ICT) compounds.1 For
example, in the D/A molecules BSC and BEC containing carbazole moieties as their D moieties
and a NO2-substituted benzothiadiazole as their A moiety, X-ray crystal data elucidated multiple
intermolecular interactions in these systems.2 These interactions were the main driving forces
directing the self-organization of the microstructures, with the different linkages exhibiting
distinctly different self-assembly behavior. Most D/A-substituted compounds suffer from
aggregation-caused emission quenching (ACQ) in the solid phase, greatly limiting their
applications.3 We have observed aggregation-induced emission (AIE) effects for several of our ICT
compounds, including the carbazole- and benzothiadiazole-based BSE, BEC, BTN-6 and BTN-7.
These prepared nanostructures exhibit green, yellow, and especially red emissions. In addition, the
distance-dependent photoluminescence image of a single microrod of BTN-7 measured using a
near-field scanning optical microscope indicated that these microrods possess outstanding optical
waveguide properties, with a waveguide efficiency (a) of 0.018 dB μm–1 and no obvious red-shift.4
References
1. Liu, H.; Xu, J.; Li, Y.; Li, Y. Acc. Chem. Res. 2010, 43(12), 1496–1508.
2. Chen, S.; Qin, Z.; Liu, T.; Wu, X.; Li, Y.; Liu, H.; Song, Y.; Li, Y. Phys. Chem. Chem. Phys.,
2013, 15, 12660–12666.
3. Xu, J.; Zheng, H.; Liu, H.; Zhou, C.; Zhao, Y.; Li, Y.; Li, Y. J. Phys. Chem. C 2010, 114, 2925–
2931.
4. Chen, S.; Chen, N.; Yan, Y.; Liu, T.; Yu, Y.; Li, Y.; Liu, H.; Zhao, Y.; Li, Y. Chem. Commun.,
2012, 48, 9011–9013.
94
OC34
DENDRIMERS AND BIOMASS: SYNTHESIS, CATALYSIS AND
ENCAPSULATION
S. Bouquillon, B. Menot, J. Stopinski
ICMR, Universitй Reims Champagne Ardenne
For several years, our research team is interested in the development of new families of dendrimers
using organic by-products from biomass (pentoses, glycerin or corresponding by-products). Some
glyco-or glycerodendrimers derived from PPI (polypropylene imines) were already obtained, and
valued in the domains of aqueous catalysis and encapsulation of metallic salts or emergent
pollutants [1,2].
Glycodendrimers were also previously synthetized and used for the preparation and the stabilization
of metallic nanoparticles (Pt, Pd, Au), which could be used in aqueous catalysis [3].
The objective of this presentation is, at first, to describe the synthesis of nitrogenous
glycerodendrimers derived of polypropyleneimines (PPis) or of polyAmidoAmines (PAMAMs)
and, secondly, to demonstrate their potential in catalyses of hydrogenation and oxidation in the
water and in encapsulation of organic pollutants (Figure 1).
Figure 1: Catalysis and encapsulation in biomass derived dendrimers
[1] C. Hadad, J-P Majoral, J. Muzart, A-M Caminade, S. Bouquillon, Tetrahedron Lett. 2009, 50,
1902.
[2] S. Balieu, A. El Zein, R. De Sousa, F. Jérôme, A. Tatibouët, S. Gatard, Y. Pouilloux, J. Barrault,
P. Rollin, S. Bouquillon, Adv. Synth. & Catal. 2010, 352, 1826.
[3] a) S. Gatard, L. Liang, L. Salmon, J. Ruiz, D. Astruc, S. Bouquillon, Tetrahedron Lett. 2011, 52,
1842. b) S. Gatard, L. Salmon, C. Deraedt, J. Ruiz, D. Astruc, S. Bouquillon Eur. J. Inorg.
Chem. 2014, 2671.
95
OC35
BIOINSPIRED CHIRAL IONIC LIQUIDS AS INNOVATIVE
ORGANOCATALYSTS
L.C. Branco
REQUIMTE, Departamento de Quнmica, Faculdade de Ciкncias e Tecnologia, Universidade Nova
de Lisboa, 2829-516 Caparica, Portugal
Chiral Ionic Liquids (CILs) can be useful as chiral solvents or chiral selector in some cases [1].
Recent examples showed the possibility to use chiral ILs as efficient organocatalysts or chiral
ligands for Asymmetric Aldol and Michael additions as well as Sharpless dihydroxylation of
olefins, among others [2,3]. Asymmetric organocatalysis is an intensively developing area of
current organic chemistry in recent years [4]. Aldol and Michael reactions play an important role in
carbon-carbon bond forming reaction. The interest of chiral molecules as novel catalysts remains to
grow as a wide range of small organic molecules, including L-aminoacids moieties such as Lproline and L-cysteine, which showed to be efficient organocatalysis for asymmetric reactions [5].
In this context, we have been developed novel Bioinspired chiral ionic liquids based on L-cysteine
and L-proline derivatives as well as task-specific nucleotides in order to test as chiral organocatalyst
of asymmetric organocatalysis and metal catalysis. direct aldol reactions between ketones with
nitrobenzaldehydes. For some cases, it was possible to obtain the pure chiral products in good
yields and enantiomeric excesses comparable with the conventional systems. Asymmetric direct
aldol reactions, Michael additions, Suzuki and Mannich reactions using some bioinspired CILs as
chiral catalyst were also tested. Catalytic recycling processes have been performed using efficient
sustainable methodologies.
Bioinspired
Chiral Ionic Liquid
Chiral
Recognition
Asymmetric
catalysis
Acknowledgements: This work has been supported by FCT/MCTES (PEst-C/EQB/LA0006/2011,
PTDC/CTM/103664/2008 and PTDC/CTM-NAN/120658/2010 projects)
References:
[1] J. Ding, D. W. Armstrong, Chirality 2005, 17, 281.
[2] a ) A. Lu, T. Liu, R. Wu, Y. Wang, G. Wu, Z. Zhou, J. Fang, C. Tang, J. Org. Chem. 2011, 76,
3872. b) L. C. Branco, P. M. P. Gois, N. M. T. Lourenco, V. B. Kurteva, C. A. M. Afonso, Chem
Comm. 2006, 2371.
[3] a) L. C. Branco, A. Serbanovic, M. N. Ponte, C. A. M. Afonso, ACS Catal. 2011, 1, 1408. b) .
C. A. M Afonso, L. C. Branco, N. R. Candeias, P.M.P. Gois, N. M. T. Lourenço, N. M. M.
Mateus, J. N. Rosa, Chem. Commun. 2007, 2669.
[4] K. Bica, P. Gaertner, Eur. J. Org. Chem. 2008, 3235.
[5] B. List, R. A. Lerner, C. F. Barbas III, J. Am. Chem. Soc. 2000, 122, 2395.
96
OC36
THE COMPARISON OF COMPUTATIONAL METHODS FOR THE STUDY
OF PYRANOSIDE-INTO-FURANOSIDE REARRANGEMENT
A.G. Gerbst, V.B. Krylov, D.A. Argunov, N.E. Nifantiev
N.D. Zelinsky Institute of Organic Chemistry RAS, Laboratory of Glycoconjugate Chemistry,
Moscow, Russia
Furanoside units are often encountered in biologically important complex polysaccharides and
smaller oligosaccharides. On the other hand, synthetic methods of furanoside modification are less
developed than those for pyranosides. Thus a promising strategy for the introduction of a furanoside
moiety into a complex saccharide might be to synthesize first the corresponding pyranoside and
then convert it into the pyranoside. Recently, in our laboratory we have discovered a novel
rearrangement that allows such transformation of a pyranoside into furanoside (PIF) with good
yields. This reaction proceeds under per-sulfation conditions in the acid media.
In this communication we present the comparison of different quantum chemical methods for the
computational study of the PIF mechanism (Fig. 1). It includes the energy calculations of starting
molecules and supposed transition states (TS) and intermediates. Obtained data are correlated with
the observed reaction kinetics.
TS2
TS1
O3S
-
post-reaction complex
HOH2C
-
-
-
HOH2C
OSO3
HO3SO
-
-
Figure 1. Proposed mechanism of the PIF transformation.
Ab initio calculations were used in this work with different split-valence basis sets. Taking 6-31G
type basis sets we varied number of diffuse and polarization functions in order to find the optimal
basis set, which would allow fast calculation with reasonable accuracy. Finally basis set 6-31+G*,
having one diffuse and one polarization function was found to give most satisfactory results.
Acknowledgement. This work was supported by the grant from Division of Chemistry and
Material Sciences of Russian Academy of Sciences, Program 1.
97
OC37
GOLD(I) CATALYSED ASYMMETRIC HYDROAMINATION OF
ALKENES IN MILD CONDITIONS
F. Agbossou-Niedercorn1, M.A. Abadie1, F. Medina1, X. Trivelli2, F. Capet1, C. Michon1
1 - University Lille Nord de France, UCCS UMR 8181 CNRS, ENSCL C7 CS90108, 59652
Villeneuve d Ascq Cedex, France
2 - University Lille Nord de France, LGSF UMR 8576, USTL 59655 Villeneuve d Ascq Cedex,
France
Gold catalysed hydroamination reactions were recently highlighted on alkenes,1a,b allenes1c and
dienes1a,d substrates for both intra- and intermolecular reactions. However, achieving highly
selective gold catalysed hydroamination of alkenes, activated or not, remains a challenging
endeavor and we would like to report herein our last results.2
First, following our researches on activated alkenes2a,b and allenes,2c the intramolecular gold(I)
catalysed asymmetric hydroamination of alkenes was studied screening a wide range of
monophosphines. Specially designed phosphoramidite ligands proved to lead to active mononuclear
gold(I) catalysts when combined with silver salts. Indeed, chiral amines were obtained in high
yields and average enantioselectivities using mild reaction conditions (Scheme 1).2d
Second, various binuclear gold(I) catalysts based on selected diphosphine ligands were studied.
When combined with a silver salt, a specific gold(I) species proved to perform efficiently the
intramolecular hydroamination of alkenes at mild temperatures with high yields and
enantioselectivities (Scheme 1).2e The molecular structure of catalyst was determined by X-Ray
diffraction analyses and DOSY NMR experiments in order to check the influence of silver salts and
water.3 Indeed, water proved to enhance significantly reaction yields and enantioselectivities.
Scheme 1.
1 (a) X. Giner, C. Nájera, G.Kovács, A. Lledós, G. Ujaque, Adv. Synth. Catal. 2011, 353, 3451; (b) M.
Kojima, K. Mikami, Synlett 2012, 23, 57; (c) K. L. Butler, M. Tragni, R. A. Widenhoefer, Angew. Chem.
Int. Ed. 2012, 51, 5175; (d) O. Kanno, W. Kuriyama, J. Z. Wang, D. F. Toste, Angew. Chem. Int. Ed.
2011, 50, 9919;
2 (a) F. Medina, C. Michon, F. Agbossou-Niedercorn, Eur. J. Org. Chem. 2012, 6218; (b) F. Medina et al.,
Comptes Rendus Chimie 2013, 16, 311; (c) C. Michon, F. Medina, M.-A. Abadie, F. AgbossouNiedercorn Organometallics 2013, 32, 5589; (d) C. Michon, M.-A. Abadie, F. Medina, F. AgbossouNiedercorn Catalysis Today 2014, doi 10.1016/j.cattod.2014.01.030; (e) M.-A. Abadie, X. Trivelli, F.
Medina, F. Capet, F. Agbossou-Niedercorn, C. Michon, submitted.
3 (a) A. Homs, I. Escofet, A. M. Echavarren, Org. Lett. 2013, 15, 5782; (b) Y. Tang, B. Yu, RSC Adv.
2012, 2, 12686; (c) D. Wang, R. Cai, S. Sharma, J. Jirak, S. K. Thummanapelli, N. G. Akhmedov, H.
Zhang, X. Liu, J. L. Petersen, X. Shi, J. Am. Chem. Soc. 2012, 134, 9012.
98
OC38
SUPRAMOLECULAR GELS FOR CATALYTIC TRANSFORMATIONS
AND NANO-MATERIALS SYNTHESIS
S. Vatsadze, V. Nuriev, A. Medved’ko
Chemistry Department, Lomonosov Moscow State University
Supramolecular gels are gels formed by immobilizations of liquid phase on the 3D network of
entangled nano-fibres which themselves are the result of supramolecular polymerization and selforganization [1]. In this report we will focus on the following:
1. supramolecular gels belongs to the family of «smart materials» since they could change their
structures in response to the external stimuli;
2. the control over structural and practical properties of gels could be engineered at the stage of
molecule design;
3. the possibility of using the organogel as a template for the synthesis of the inorganic replica;
4. post-synthetic transformations, i.e. supercritical fluid drying, expands the scope of materials
properties;
5. metal-containing supramolecular gels combine the properties of both heterogeneous and
homogeneous catalysts.
We thank financial support by RFBR (grant #14-03-91160).
1. V.P.Ananikov, L.L.Khemchyan, Yu.V.Ivanova, V.I.Bukhtiyarov, A.M.Sorokin, I.P.Prosvirin,
S.Z.Vatsadze, A.V.Medved'ko, V.N.Nuriev, A.D.Dilman, V.V.Levin, I.V.Koptyug,
K.V.Kovtunov,
V.V.Zhivonitko,
V.A.Likholobov,
A.V.Romanenko,
P.A.Simonov,
V.G.Nenajdenko,
O.I.Shmatova,
V.M.Muzalevskiy,
M.S.Nechaev,
A.F.Asachenko,
O.S.Morozov, P.B.Dzhevakov, S.N.Osipov, D.V.Vorobyeva, M.A.Topchiy, M.A.Zotova,
S.A.Ponomarenko,
O.V.Borshchev,
Y.N.Luponosov,
A.A.Rempel,
A.A.Valeeva,
A.Yu.Stakheev,
O.V.Turova,
I.S.Mashkovsky,
S.V.Sysolyatin,
V.V.Malykhin,
G.A.Bukhtiyarova, A.O.Terent'ev, I.B.Krylov. "Development of new methods in modern
selective organic synthesis: preparation of functionalized molecules with atomic precision",
Russ.Chem.Rev., 2014, 83 (10), in press. DOI: 10.1070/RC2014v083n10ABEH004471
99
OC39
SYNTHESIS AND TRANSFORMATIONS OF STRAINED POLYNITROGEN
COMPOUNDS
M.A. Kuznetsov, A.S. Pankova
Saint Petersburg State University, Institute of Chemistry, Saint Petersburg, Russia
The oxidation of many N-aminoheterocycles in the presence of unsaturated compounds is a general
way to N-aminoaziridine derivatives containing a strained three-membered ring and combining two
heterocyclic moieties in one molecule via a weak N-N bond. This reaction, the so-called oxidative
aminoaziridination, is applicable to a wide range of unsaturated substrates and proceeds in a
stereospecific manner with a complete retention of a spatial arrangement of substituents at >C=C<
bond in the resulted N-aminoaziridines. In this way we have synthesized a set of alkynylaziridines,
which possess three endothermic fragments in one molecule, and large series of adducts to styrenes,
unsaturated carbonyl compounds, a lot of spiroaziridines etc.
With alkenylpyrazoles the expected heterocyclic chains are usually formed in good yields. And it
was the same for alkenyl-1,2,4- and 1,3,4-oxadiazoles with one or two double bonds in the side
chains. The reaction with alkenylfuranes leads to the unsaturated acyclic compounds exclusively,
and can be used for a stereospecific synthesis of 4-oxohexa-2,5-dienal derivatives with
(Z)-configuration of 2,3-C=C bond. The oxidative aminoaziridination of the very similar alkenylthiophenes leads to expected adducts onto exocyclic C=C bond, but with thiophene itself and even
with selenophene gave the very interesting tricyclic diadducts, though in low yields.
Since the classical works of R. Huisgen in 60-ies it is well known that the C-C bond in aziridines
can be broken thermally or upon irradiation giving the octet-stabilized 1,3-dipoles, so-called
azomethyne ylides, which can be involved in 1,3-dipolar cycloaddition reactions. We have found
that for cis- and trans-2,3-disubstituted 1-phthalimidoaziridines this set of transformations proceeds
in a stereospecific manner as a concerted process which obeys the rules of orbital symmetry
conservation. The intramolecular cycloaddition of 1,3-dipoles should lead to the polycyclic
condensed compounds, which are of interest in many aspects. And we have realized it for some Nphthalimidoaziridines with sterically accessible, but inactivated C=C and C≡C bonds.
In some cases the regioisomeric imines appeared as the main components of these reaction
mixtures. This result caused by 1,2-migration of phthalimidyl rest in the intermediate ylides is often
the general one for arylsubstituted aziridines. On another hand, an attempt for intramolecular
cycloaddition of aziridines with carbonyl substituents led to quite another products: the 1,5electrocyclization of an intermediate ylide with a participation of C=O bond followed by loss of
phthalimide fragment provided aromatic oxazoles in good yields. This transformation of carbonylsubstituted azomethyne ylides into oxazoles competes with an intermolecular cycloaddition too.
The yields of oxazoles in all these reactions usually vary from good up to excellent. Taking it into
account we have offered the simple and efficient transformation of α,β-unsaturated carbonyl
compounds into the corresponding oxazoles via N-phthalimidoaziridines or even via N-arylsulfonylaziridines. This approach is applicable to the synthesis of oxazoles with ethynyl substituent
as well. In the case of C-alkenylaziridines, the intermediate ylide contains a conjugated C=C bond,
and another kind of 1,5-electrocyclization – into pyrrolines – is conceivable.
Combination of the strained three-membered rings and hydrazine moiety makes cyclopropylhydrazines highly energetic compounds. Beside it, the hydrazine fragment occurs in a variety of
bioactive compounds. But only two – mono- and 1,2-dicyclopropylhydrazine – out of five possible
cyclopropylhydrazines have been known till now. And the last part of our work is devoted to the
synthesis of still unknown cyclopropylsubstituted hydrazines.
This work was supported by Russian Scientific Fond (research grant no. 14-13-00126).
100
OC40
NEW TYPE OF REACTIVITY OF DONOR-ACCEPTOR
CYCLOPROPANES: GaCl3-MEDIATED GENERATION OF FORMAL 1,2AND 1,4-DIPOLES
R.A. Novikov, A.V. Tarasova, Y.V. Tomilov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp.,
119991 Moscow, Russian Federation
A new type of reactivity of donor-acceptor cyclopropanes has been discovered. On treatment with
anhydrous GaCl3, they react as sources of even-numbered 1,2- and 1,4-dipoles instead of the
classical odd-numbered 1,3-dipoles due to migration of positive charge from the benzyl center. This
type of reactivity has been demonstrated for new reactions, viz., cyclodimerizations of donoracceptor cyclopropanes that occur as [2+2]-, [3+2]-, [4+2]-, [5+2]-, [4+3]-, and [5+4]-annulation.
The [4+2]-annulation of 2-arylcyclopropane-1,1-dicarboxylates to give polysubstituted 2aryltetralins has been developed in a preparative version that provides exceedingly high regio- and
diastereoselectivity and high yields. The strategy for selective cross-combination of donor-acceptor
cyclopropanes was also been developed. The mechanisms of the discovered reactions involving the
formation of a comparatively stable 1,2-ylide intermediate have been studied. Hitherto unknown
complexes of donor-acceptor cyclopropanes with GaCl3 belonging to a new type and having a 1,2dipole (ylide) structure have been obtained and characterized by 1D, 2D and DOSY NMR
spectroscopy. Futher transformations of this complex have also been demonstrated.
N e w 1 ,2 - a n d 1 ,4 -D ip o la r
S y n th e t ic E q u iv a le n ts
G a C l3
C O 2M e
Ar
M e O 2C
C O 2M e
M e O 2C
C O 2M e
Ar
C O 2M e
M e O 2C
C O 2M e
C la s s ic a l 1 , 3 -D ip o le
R
Ar
[2 + 2 ]
[4 + 2 ]
R5
C O 2M e
R4
C O 2M e
R3
M e O 2C
C O 2M e
M e O 2C
R1
R2
C O 2M e
Ar
Ar
The discovered [4+2]-annulation of DAC is a synthetically valuable process that allows the onestage assembly of polysubstituted tetralins with exceptionally high regio- and diastereoselectivity.
The latter may be of interest as synthons in organic synthesis and as compounds possessing
biological activity. In fact, the aryltetralin moiety occurs in the structures of a number of
compounds that have been isolated from various natural sources and manifest a broad spectrum of
biological activity, including antitumor activity.
This work was supported by the Russian Federation President Council for Grants (Program for
State Support of Leading Scientific Schools of the Russian Federation, grant no. NSh-604.2012.3)
Selected Publications:
Tetrahedron Lett., 2011, 52, 4996–4999; Organometallics, 2012, 31, 8627–8638;
J. Org. Chem., 2012, 77, 5993–6006; Org. Lett., 2013, 15, 350–353;
Helv. Chim. Acta., 2013, 96, 2068–2080; Angew. Chem. Int. Ed., 2014, 53, 3187–3191.
101
OC41
NEW REACTIONS OF TANTALUM(V) AMIDES
M.N. Sokolov, A.L. Gushchin, A.V. Rogachev, P.A. Abramov
Nikolaev Institute of Inorganic Chemistry
Transition metal amides are highly reactive compounds which are much employed as reagents,
ligand transfer agents, or precursors for more complex molecules. The ready cleavage of the highly
polar M-NR2 bond makes the amides particularly important synthons for a wide range of new
compounds and materials. The M-NR2 bond can be easily cleaved by protonation using various
reagents with acidic E-H bonds (alcohols, thiols, secondary phosphines, pyrazoles etc.). Reactive
small molecules such as CS2 or CO2 undergo insertion with the formation of dithiocarbamates and
carbamates. In this work we report synthesis of new Ta coordination compounds and clusters by
reactions of Ta(NMe2)5 with CS2, Ph2PH and pyrazol; with or without subsequent treatment with
sulfur. Ta(NMe2)5 easily react with CS2 with the formation of [Ta(S2CNMe2)3( -CH2-NMe)] (1).
The formation of 1 can be explained as triple insertion of CS2 followed by α-elimination of a
HNMe2 molecule. Excess of CS2 leads to the formation (in CH2Cl2) of [Ta(S2CNMe2)4]Cl (2).
Cyclic voltammetry shows that [Ta(S2CNMe2)4]+ can be reversibly reduced to the neutral
[Ta(S2CNMe2)4], the Ta(V)/Ta(IV) couple having E1/2 – 0.74 V vs. Ag/AgCl. Reaction with CS2 in
the presence of S8 leads to a complex mixture of Ta(V) dithiocarbamates [TaS(S2CNMe2)3] (3),
[Ta(S2)(S2CNMe2)3] (4), and a perthiocarbamate complex [TaS(S3CNMe2)(S2CNMe2)2] (5).
HPPh2 rapidly reacts with Ta(NMe2)5 with the formation of an unstable product, which after
treatment with S8 yields green crystals of a cuboidal cluster, [Ta4S4(μ-S2PPh2)4(S2PPh2)2] (6), which
is, to the best of our knowledge, the first cluster with the {Ta4S4} core. Long Ta-Ta distances (2.973.05 Å) correspond to electron-deficient (only six of the required 12 e) M-M bonding in the cluster
core.
3,5-dimethylpyrazol (PzH) is a stronger N-H acid than Me2NH, and reacts with Ta(NMe2)5 with the
formation of yellow crystals of the pentakis(pyrazolate), [Ta(pz)5] (7). According to X-ray data, the
Ta atom achieves CN 8 by coordinating three pz ligands in the 2, and two pz ligands in the 1
mode. All the compounds have been characterized by single crystal X-ray analysis. Reactivity of
complexes 1-7 is being investigated.
The work was supported by RFBR grant No. 12-03-33028.
[1] M.F. Lappert, A. Protchenko, P. Power, A. Seeber. Metal-Amide chemistry, 2009, John Wiley
and Sons, 355 pp.
102
OC42
STRUCTURE-REACTIVITY RELATIONSHIPS IN THE REACTIONS OF CAMINO-1H-1,2,4-TRIAZOLES WITH ELECTROPHILES
V.M. Chernyshev, D.A. Pyatakov, A.V. Astakhov, A.I. Evdokimova, A.Yu. Chernenko
Platov South-Russian State Polytechnic University (NPI), Novocherkassk, Russia
Molecules of C-amino-1,2,4-triazoles (AT) contain several alternative nucleophilic centers, namely
NH2 group and any of the ring nitrogen atoms, and therefore can be considered as multifunctional
nucleophilic reagents. Such multifunctionality, on the one hand, opens up exciting possibilities for
the synthesis of various substituted triazoles and condensed heterocycles [1], however, on the other
hand, it causes the problem of selectivity [2, 3]. The present report discusses relationships between
the structure of AT and their reactivity towards electrophiles and some novel approaches to the
control of selectivity.
On the basis of computational and experimental methods it was established that the position of the
endocyclic substituent R has a significant influence on the reactivity of C-amino-1-R-1,2,4triazoles. The global nucleophilicity of the 1-substituted 3-amino-1,2,4-triazoles is higher than the
1-substituted 5-amino-1,2,4-triazoles. Therewith, amino group in the position 3 of triazole ring is
substantially more nucleophilic than in the position 5. The atoms N-2 and N-4 of triazole ring as
well as the 3-NH2 group are the most favorable sites in the 1-substituted C-amino-1,2,4-triazoles for
the attack of electrophiles.
Some new approaches to the selective synthesis of substituted triazoles and condensed heterocycles
via reactions of AT with electrophilic and bielectrophilic reagents are considered. The structural
features and reactions of condensed derivatives of 1,2,4-triazole including some new recyclizations
are discussed.
Acknowledgements This work was financially supported by the Russian Foundation for Basic
Research (grant no. 13-03-00253) and in part by the Ministry of Education and Science of the
Russian Federation, State contract No. 2014/143 (project No. 2945).
References
[1] Curtis, A.D.M.; Jennings, N. 1,2,4-Triazoles. In Comprehensive Heterocyclic Chemistry III. Elsevier:
Oxford, 2008. V. 5. P. 159-209.
[2] Chernyshev, V.M.; Astakhov, A.V.; Starikova, Z.A. Tetrahedron 2010, 66, 3301.
[3] Chernyshev, V.M.; Pyatakov, D.A.; Sokolov, A.N.; Astakhov, A.V.; Gladkov, E.S.; Shishkina, S.V.;
Shishkin, O.V. Tetrahedron. 2014, 70, 684.
103
OC43
SILYL NITRONATES IN THE NOVEL [3+3]-CYCLOADDITION
REACTION WITH DONOR-ACCEPTOR CYCLOPROPANES
A.A. Mikhaylov1, R.A. Novikov1, D.E. Arkhipov2, S.L. Ioffe1
1 - N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russian
Federation
2 - A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
Moscow, Russian Federation
Cycloaddition reactions are one of the most effective tools for rapid generation of molecular
complexity.1 Recently, the formal cycloadditions have evoked special attention due to the intriguing
ability of donor-acceptor cyclopropanes, mainly 1,1-cyclopropane diesters 1, to behave as
equivalents of 1,3-zwitterions under Lewis acid catalysis.2,3 The formal [3+3]-cycloaddition,
discovered by Kerr and co-workers on the nitrones in 2003,4 has already proved itself as a powerful
method for six-membered cycles construction.3
In this respect, silyl nitronates 2 can be considered as perspective substrates for formal
cycloaddition chemistry due to their 1,3-dipolaric nature. We have shown that different silyl
nitronates 2 derived from both primary and secondary nitro compounds can react with 1,1cyclopropane diesters 1 giving rise to polysubstituted six-membered nitroso acetals 3.5 The latters
in hand can be easily transformed into isomeric pyrroline-N-oxides 4 and 5 via novel acid-catalyzed
ring contraction/silanol elimination reaction.
In the presentation the major regularities of the observed [3+3]-cycloaddition reaction will be
discussed. The special attention will be focused on the reasons determining stereochemical outcome
of nitroso acetals 3.
The work was supported by Russian Foundation for Basic Research (Grants #12-03-00278, 14-0331560).
References
1. M. Juhl, D. Tanner, Chem. Soc. Rev. 2009, 38, 2983-2992.
2. C. A. Carson, M. A. Kerr, Chem. Soc. Rev. 2009, 38, 3051-3060.
3. T. F. Schneider, J. Kaschel, D. B. Werz, Angew. Chem. Int. Ed. 2014, 53, 5504–5523.
4. I. S. Young, M. A. Kerr, Angew. Chem. Int. Ed. 2003, 42, 3023-3026.
5. A. A. Mikhaylov, R. A. Novikov, Yu. A. Khomutova, D. E. Arkhipov, A. A. Korlyukov, A. A.
Tabolin, Yu. V. Tomilov, S. L. Ioffe, Synlett, submitted.
104
OC44
SOLID-PHASE SYNTHESIS OF PINCER COMPLEXES: EMERGING
ALTERNATIVE TO CONVENTIONAL SYNTHESIS IN SOLUTION
D.V. Aleksanyan, V.A. Kozlov
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
Pincer complexes featuring a tridentate monoanionic framework have become a privileged class of
organometallic compounds, finding extensive application in catalysis, materials science,
biochemistry and so on.1,2 Several synthetic routes, including direct cyclometalation, oxidative
addition, and trans(cyclo)metalation, give access to pincer complexes with almost any type of
ligands and metal ions, however, the simplest route seems to be direct cyclometalation. Numerous
examples of direct cyclometalation of pincer ligands have been described in solution, but the
literature data on the solid-state synthesis of metallacycles are restricted only to several reports
dealing with the thermally induced intramolecular cyclometalation of well-defined coordination
complexes leading to monometallacyclic species. Recently we have shown that cyclometalation of
pincer ligands can be readily carried out in the solid state simply by heating homogeneous mixtures
of a ligand and metal precursor obtained by manual grinding in a mortar. 3 This novel solid-phase
approach has now been extended to a range of pincer-type ligands which require the activation of
the C–H, N–H, and O–H bonds and have different ancillary S-, P-, and N-donor groups (for
selected examples see figure). The results obtained show great potential of the solid-phase
cyclometalation as an alternative to the conventional synthesis of complex organometallic
compounds in solution. Some aspects of the solid-phase cyclometalation will be discussed based on
the results of spectral and thermochemical analyses.
Ph
Ph
P
Ph
Ph P
S
N
N
S
Pd
Cl
O
Pd
S
Cl
S
HN
Ph
P h2P
Ph
P
S
Pd
N
Cl
Cl
Pd
N
S
S
Me
Ph
Ph
P
O
S
Cl
Pd
N
O
S
P
Ph
Ph
This work was supported by the Russian Foundation for Basic Research (project no. 14-03-31237mol-a) and the Grant of the President of the Russian Federation for young scientists (project no.
MK-382.2014.3).
1. The Chemistry of Pincer Compounds, D. Morales-Morales and C. M. Jensen (Eds.), Elsevier,
New York, 2007.
2. Organometallic Pincer Chemistry, G. van Koten and D. Milstein (Eds.), Topics Organomet.
Chem., 2013, 40.
3. V. A. Kozlov, D. V. Aleksanyan, M. V. Korobov, N. A. Avramenko, R. R. Aysin, O. A.
Maloshitskaya, A. S. Korlyukov and I. L. Odinets, Dalton Trans., 2011, 40, 8768.
105
OC45
SYNTHETIC APPROACHES AND ELECTRONIC PROPERTIES OF
FUNCTIONALIZED FULLERENES AS NANOSIZED OPTICAL
MOLECULAR SWITCHES
L.M. Khalilov, A.R. Tuktarov, A.R. Akhmetov, A.A. Khuzin, Z.R. Shakirova, A.R. Tulyabaev, I.I.
Kiryanov, V.M. Yanybin, U.M. Dzhemilev
Institute of Petrochemistry and Catalysis of RAS
At present, the abilities of the manufacturing technology of traditional materials for modern
computers have almost peaked. The main factor that restrains creation of modern supercomputers is
a critical size of silicon transistors to be reached which are responsible for a quick response. One
possible way to solve the problem is to replace conventional silicon transistors by molecular
switches that can be by several orders less than the known smallest devices.
Given that the molecular switches must have π-donor groups along with π-acceptor one, we have
put forward the idea to use fullerene derivatives, a new allotropic carbon form, that possess high
donor-acceptor features. Thus, a new effective methods of synthesis of potential molecular switches
and three-dimensional memory elements based on C60 and C70 fullerene derivatives have been
suggested. Highly selective methods of cycloaddition of organic azides to fullerenes under metalcomplex catalysts have been developed. This gives the individual aziridine- and azahomofullerenes
that able to isomerize into each other under influence of UV irradiation.
Algorithms of dichotomous features which are responsible for photochromic properties of
molecular switches and generating of the new structures with incorporated fullerenes as doping
agents directly into the fullerene core and in the attached moieties to activate the donor-acceptor
properties and stability of molecular electronic systems. The results of molecular design of new
types of optical molecular switches will be done using calculations of the electronic structure and
physicochemical properties of fullerene derivatives with modern high-level quantum chemistry
approaches (DFT and ab initio) will be discussed.
106
OC46
COORDINATION CHEMISTRY OF BIS(PYRAZOLYL)PYRIDINES WITH
3d-TRANSITION METALS: RECENT DEVELOPMENT AND PROGRESS
N.M. Kurnosov
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
Coordination compounds of transition elements with N-donor ligands are widely used as catalysts, molecular
switches (SCO), dye-synthesized solar cell (DSSC). As analogs of terpyridine 2,6-bis(pyrazolyl)pyridines
are widely investigated and there are known a lot of results in coordination chemistry of them [1]. Most of
results are related to iron complexes and investigation of spin-crossover.
The aim of this work is the synthesis and study of complexes of 3d-transition elements with 2,6bis(pyrazolyl)pyridines. A large library of such ligands has been synthesized. There are two major branches
of research – copper complexes and iron binuclear complexes with 3,6-bis(pyrazolyl)-1,2,4,5-tetrazine as
bridging ligand. It is common fact that such iron complexes can exhibit two-step spin-crossover transition
from e.g. HS-HS state to the LS-LS state and also mix-valent species can be stabilized. Also for copper biand polynuclear complexes are much interesting due to the possibility of metal-metal interaction.
The resulted complexes were investigated by ESR spectroscopy, electron spectroscopy, mass spectrometry,
Fig. 1. Structures of
[Cu(Cl)(bPzPy)]2(ClO4)2 (left) and
[Cu(Cl)(bPzPy)(ClO4)] (right).
Fig. 2. The 1D-chains for complex
[Cu(bPzPy)(H2O)(NO3)2], hydroden bonds are
maked by dotted lines. View along the b axis.
infrared and Raman spectroscopy, their magnetic properties were measured and calculated by quantumchemical qualculations. For some complexes crystals suitable for X-ray structure analysis were obtained. In
the case of iron and cobalt complexes of 2,6-bis(pyrazolyl)pyridines have a monomeric structure regardless
of counterions and the introduction of additional ligands capable of acting as bridging ligands – halide- and
azide- anions. Dimeric complexes with bridging ligands could be obtained for copper and nickel. There is a
weak ferromagnetic interaction for dimeric copper complexes with the structure [Cu(Cl)(bPzPy)]2(ClO4)2
(Fig 1.), calculated coupling constant for which is in agreement with the experimental data. For nonsubstituted pyrazole one-dimensional chain with perchlorate-bridging was obtained in the first time (Fig 1.).
In some cases 1D-chains or more complicated frameworks are formed by hydrogen bonding (Fig 2.) [2].
Dinuclear iron complexes has been obtain with 3,6-bis(pyrazolyl)-1,2,4,5-tetrazine as bridging ligand and
2,6-bis(pyrazolyl)pyridines the simple ligands. The ground state and possibility of stable mix-valent state
depend on the structure of 2,6-bis(pyrazolyl)pyridines.
The author thanks Prof. S.I. Troyanov, Prof. Yu.M. Kiselev, Cand.Sc. V.D. Dolzhenko, V.V. Korolev and
his students A.A. Vuhovskiy, T.D. Ksenofontova and A.G. Gevondyan.
1. M.A. Halcrow, Coord. Chem. Rev. 2005, 249, 2880–2908.
2. Dolzhenko, V. D., Kurnosov, N. M. and Troyanov, S. I. (2014), Z. anorg. allg. Chem., 640: 347–352.
107
OC47
POLYMER-STABILIZED PALLADIUM NANOPARTICLES AS EFFECTIVE
CATALYSTS OF SELECTIVE HYDROGENATION OF ALKINOLS
L.Zh. Nikoshvili1, V.G. Matveeva1, E.M. Sulman1, B.D. Stein2, L.M. Bronstein3
1 - Tver Technical University, 170026, Tver, Russia
2 - Indiana University, Department of Biology, IN 47405, Bloomington, USA
3 - Indiana University, Department of Chemistry, IN 47405, Bloomington, USA; King Abdulaziz
University, Jeddah 21589, Saudi Arabia
Selective hydrogenation of unsaturated carbon-carbon bond using Pd nanoparticles (NPs) is of great
importance as widely applicable in synthesis of fine chemicals, vitamins and pharmaceuticals. One
of the most complicated problems along with achieving of high activity, selectivity and stability of
catalytic system is control over the Pd NP size, size distribution and morphology [1, 2]. To achieve
appropriate selectivity, traditional industrial catalysts of alkyne hydrogenation require the addition
of modifiers, which are not desirable for environment [3-5]. Though, in the case of terminal
alkynes, neither the control of NP morphology [2] nor modification [4] yield the benefits, NP size
and stabilizing environment play crucial role and the selectivity problem still exists [5].
Among the organic porous supports for catalyst synthesis, hypercrosslinked polystyrene (HPS)
received increased attention due to its high crosslinking degree, which can be higher than 100%.
The unique property of HPS is the ability to swell in different solvents, which favors inclusion of
various organometallic compounds in the HPS matrix. Besides, HPS based catalysts allow control
of the NP formation due to a “cage” effect (by limiting the NP size with the pore size) along with
controlling the precursors and reduction conditions.
In this work the incorporation of Pd NPs in polymeric matrix of HPS at variation of metal loading,
precursor nature and type of polymer (influence of fictionalization) is discussed. Series of Pd/HPS
catalysts was tested in the reaction of selective hydrogenation of 2-methyl-3-butyne-2-ol, which is
intermediate of synthesis of fragrant substances and vitamins (E and K) and model compound of
industrially important acetylene alcohols C10 and C15. Physicochemical characterization was
performed via XPS, liquid nitrogen physisorption and TEM.
Developed catalysts were found to contain Pd NPs with mean diameter of 3-5 nm (Fig. 1) and
provide high selectivity (up to 98.5% at 100% of the substrate conversion). Besides, synthesized
HPS-based nanocomposites were highly active in comparison with traditional hydrogenation
catalyst (i.e. 2%(wt.)-Pd/CaCO3), and no leaching of catalytically active compound was observed.
Financial support was provided by Seventh Framework Programme of the European Community
(CP-IP 246095-2 POLYCAT) and Ministry of education and science of Russia (contract P1345).
References
1. N. Semagina, L. Kiwi-Minsker. Catal. Lett. 127 (2009) 334.
2. L. Kiwi-Minsker, M. Crespo-Quesada. Top. Catal. 55 (2012) 486.
3. P.W. Albers, K. Möbus, Ch.D. Frost, S.F. Parker. J. Phys. Chem. C. 115 (2011) 24485.
4. J.A. Anderson, J. Mellor, R.P.K. Wells. J. Catal. 261 (2009) 208.
5. P.T. Witte, P.H. Berben, S. Boland, E.H. Boymans, D. Vogt, J.W. Geus, J.G. Donkervoort. Top.
Catal. 55 (2012) 505.
108
OC48
CATALYTIC CARBONYLATION OF OLEFINS, ALCOHOLS AND
BENZYL HALIDES IN MOLTEN SALT MEDIUM
O.L. Eliseev, T.N. Bondarenko, A.L. Lapidus
N.D.Zelinsky Institute of organic chamistry, Moscow, Russia
Transition metal-catalyzed carbonylation of unsaturated hydrocarbons, alcohols and halides is a
direct one-step route to carboxylic acids and esters. In presented work we systematically studied
application of some molten salts such as tetrabutylammonium and 1-butyl-3-methylimidazolium
derivatives as a media for these reactions. This approach provides a number of unusual possibilities.
The most striking result is higher activity of phosphine-free palladium catalyst than that of
“traditional” Pd-phosphine complexes. Bromide-containing molten salts stabilize palladium in the
form of nano-sized suspension, as demonstrated by TEM. For unsymmetrical olefinic substrates,
regioselectivity depends on anion nature in molten salt. In particular, chloride improves selectivity
to 2-phenylpropanoic acid in carbonylation of styrene. Due to high solubility of catalyst in molten
salt, it can be used repeatedly by simple extraction of products from reaction mixture with diethyl
ether. In dodecene-1 carbonylation, ten cycles were carried out without loss of activity and
selectivity. Importantly, reloading procedure may be performed in air atmosphere. Reaction scheme
for the carbonylation of 1-phenylethanol into phenylpropanoic acids is proposed.
Hydroxycarbonylation of benzyl halides in molten salt medium proceeds fast in the absence of base.
Therefore, formation of stoichiometric amount of halide salt may be avoided.
109
Posters
110
111
P1
SYNTHESIS OF FLUORESCENT RECEPTORS VIA Pd-CATALYZED
AMINATION OF 6-BROMOQUINOLINE AND
3-BROMOPHENANTHROLINE
A.S. Abel1, A.D. Averin1, A.G. Bessmertnykh-Lemeune2, I.P. Beletskaya1
1 - M.V. Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
2 - Universite de Bourgogne, ICMUB, Dijon, France
Numerous works have been devoted to the design of new fluorescent sensors for various
applications such as clinical toxicology, environmental bioorganic chemistry and waste
management [1]. To develop optical molecular probes or sensors for toxic metals, ruthenium
complexes with ditopic 1,10-phenanthrolines seem to be an appropriate solution. Moreover,
aminoquinolines possess good fluorescent properties but have not yet been investigated as a
signaling subunit in chemosensors. In this work, Pd-catalyzed amination of 6-bromoquinoline (1)
and 3-bromo-1,10-phenanthroline (2) with linear polyamines 3a-d was investigated to prepare
fluorescent receptors.
The fluorescent derivatives of 6-aminoquinoline 4 were synthesized in good yields (up to 62%)
using Pd/BINAP system as catalyst (Scheme). The amination of 3-bromo-1,10-phenanthroline is
more complicated and Josiphos ligand should be used to obtain 3-amino-1,10-phenanthrolines 5 in
satisfactory yields (32-36%) (Scheme).
Scheme. Pd-catalyzed amination of 6-bromoquinoline (1) and 3-bromo-1,10-phenanthroline (2)
This reaction is a key step in the synthesis of fluorescent receptors 6-8 (Figure). The sensing
properties of receptors 7 and 8 in the presence of various amounts of environmentally-relevant
metal ions were evaluated by UV-vis and fluorescent spectroscopy.
Figure. Fluorescent receptors for metal ions.
Acknowledgements: The work was performed in the frames of French-Russian Associated
Laboratory “LAMREM” and financially supported by the RFBR (grant N 12-03-93107) and CNRS.
[1] A.N. Uglov, A.G. Bessmertnykh-Lemeune, R. Guilard, A.D. Averin, I.P. Beletskaya, Russ.
Chem. Rev., 2014, 83, 196.
112
P2
MECHANISM OF CARBON MONOXIDE OXIDATION OVER SUPPORTED
CuO CATALYSTS
Yu.A. Agafonov1, N.A. Gaidai1, N.V. Nekrasov1, L.C. Loc2, N. Tri2, H.T. Cuong2, H.S. Thoang2,
A.L. Lapidus1
1 - Institute of Organic Chemistry, RAS, Moscow, Russia
2 - Institute of Chemical Technology, Vietnam Acad. Sci. Techn., Ho Chi Minh City, Vietnam
Supported CuO catalysts with additives of other oxides are effective ones for CO oxidation.
Introduction of small amounts of noble metals in these catalysts allows to increase their activity
which can exceed the activity of supported platinum catalysts – the most active known ones in CO
oxidation. Designing new catalysts for this process requires depth knowledge on the reaction
mechanism. This work is devoted to the study of mechanism of CO oxidation over the following
supported on -Al2O3 catalysts: 10 (wt.) %CuO (CuAl), 10 %CuO+20% CeO2 (CuCeAl), 10
%CuO+10% Cr2O3 (CuCrAl) without and with addition of Pt. The content of Pt varied in the range
of 0.05 – 0.3 wt.%. The following physico-chemical methods were used for catalyst investigation:
BET N2-Adsorption, XRD, TPR, SEM, EDS and IR-CO adsorption. There are the surface data of
Table. Surface characteristics of the studied catalysts: studied catalysts in Table.
specific surface area (SBET), crystal size of Cu (dCu), It is seen that the Cr, Ce and Pt
dispersion of Cu (γCu ), maximum reduction enhanced the reducibility of copper
temperature (Tmax) and extent of reduction for ions catalysts what expressed in the decrease
of the reduction temperature and the
Cu2+Catalysts
(KRed, %)
SBET dCu γCu Tmax KRed increase of the reduction extent (the
%
%
m2/g nm
C
reducibility of catalysts CuAl and
Oxide Catalysts
CuCeAl was increased in 2.5 – 3 times).
CuAl
177.0 11.9 13.1 375 13.0 It was shown that the optimal Pt content
CuCrAl
166.0 15.5 10.0 355 28.4 is 0.1%. With this amount of Pt, catalyst
CuCeAl
321 17.6 PtCuCeAl was capable to convert
67.0 completely CO to CO2 at 110oC
Pt-containing oxide catalysts
o
0.1PtCuAl
95.9 11.6 13.4 274 36.7 (without Pt - at 125 C). The process
mechanism was studied by unstationary
0.2PtCuAl
95.1
0.05PtCuCrAl
89.2 18.8 8.3
308 29.9 response method. Relaxation curves,
0.1PtCuCeAl
80.1 35.2 4.4
255 45.8 describing a transition of the system to a
new steady state, were obtained by a
jump change of the corresponding concentrations. The residence time, defined as the ratio of the
reaction system volume to the flow rate, was 2-5 times lower than the turnover time. It is meant that
the observed transition phenomena were associated with the intrinsic processes. It was shown that
Pt weakened the interaction of active phase which resulted in an increase of the reaction rate. The
initial substances participated in the reaction in adsorbed state, the most part of the surface was
occupied by oxygen over all the catalysts, Ce was facilitated the mobility of oxygen. Pt was
increased the bond strengh of CO, O2 and CO2 with the surface of catalysts. Not only adsorbed
oxygen, but lattice oxygen took part in the reaction but the last oxygen in less extent. The change of
introduced glass filler in the reactor showed that reaction of CO oxidation proceeds mainly through
heterogeneous mechanism, the share of homogeneous mechanism does not exceed 15%. It was
shown that CO and O2 adsorption were quick steps, one intermediate compound was formed in
slow step of the process. The overall step-scheme of CO oxidation was proposed over studied
catalysts.
The work is supported by RFBR (№13-03-93001_Viet_a) and NAFOSTED grant № 104.03-2012.60.
113
P3
EFFICIENT CATALYTIC HYDRODEOXYGENATION OF
UNPROTECTED CYCLIC IMIDES TO CYCLIC AMINES BY
HETEROGENEOUS CATALYSIS
A.M. Maj, I. Suisse, F. Agbossou-Niedercorn
University Lille Nord de France, UCCS UMR 8181 CNRS, ENSCL C7 CS90108, 59652 Villeneuve
d Ascq Cedex, France
Cyclic amines comprising fused saturated N-heterocycles are valuable synthetic intermediates. They
are found in numerous drug candidates such as bicifadine, cytisine, gliclazide, or telaprevir to name
just a few (Figure 1). The catalytic hydrogenation of imides appears to be the most elegant and
promising reaction to produce properly and efficiently such amines. Since the reaction might
potentially lead to several compounds, it needs to be controlled by an appropriate catalyst, which
has to perform selectively two successive reductive cleavages of the C=O functionalities without
breaking the cycle.
N
O
NH
N
NH
H
N
N
pTol
O
Bicifadine
Cytisine
O O O
S
N
N
N
H
H
O
NH
H
N
O
O
O
H
N
O
Gliclazide
NH
H
Telaprevir
Figure 1. Bioactive cyclic amines.
As part of our ongoing interest for the application of catalytic hydrogenation in the preparation of
cyclic amines,[1] we became interested in the synthesis of fused N-heterocycles. Herein, we report
on the first efficient total reduction of nitrogen-unsubstituted cyclic imides in the presence of
heterogeneous catalysts generated in situ from rhodium and molybdenum carbonyls (Scheme).
Various substrates could be reduced with high selectivities and yields (both up to 100%). Platinum
catalysts proved also efficient to hydrogenate some cyclic imides. In addition, all catalysts could be
recycled at least three times without significant loss of activity. Finally, hydrodeoxygenation of a
model cyclic imide was successfully performed on a gram scale.[2]
O
O
catalyst
( )n
N H
O
solvent
( )n
OH
N H
+
( )n
N H
+
( )n
N H
PH2, T
n = 0 or 1
up to 100% yield
References
[1] a) Maj, A. M.; Suisse, I.; Méliet, C.; Agbossou-Niedercorn, F. Tetrahedron: Asymmetry 2010,
21, 2010. b) Maj, A. M.; Suisse, I.; Méliet, C.; Hardouin, C.; Agbossou-Niedercorn, F.
Tetrahedron Lett. 2012, 53, 4747. c) Maj, A. M.; Suisse, I.; Hardouin, C.; AgbossouNiedercorn, F. Tetrahedron 2013, 69, 9322.
[2] Maj, A. M.; Suisse, I.; Pinault, N.; Robert N.; Agbossou-Niedercorn, F. ChemCatChem
accepted.
114
P4
REACTIONS OF N-ALKYLHALOGENALDIMINES WITH O,ODIALKYDITHIOPHOSPHORIC ACIDS
N.G. Aksenov, R.A. Khairullin, M.B. Gazizov, R.N. Burangulova
Kazan National Research Technological University, Department of Organic Chemistry, Kazan,
Russian Federation
We found that direction of interaction of N-alkyl-2-halogenaldimines (1-2) with О,Оdialkyldithiophosphoric acids (3) mainly depends on the nature of halogen. Reaction between О,Оdialkyldithiophosphoric acids (3) and N-alkyl-2-chloroaldimines (1) was first studied by dynamic
1
Н, 13С and 31Р NMR in the temperature intervals from -60 °C to 25 °С. It was found that reaction
proceeds in two steps. At first step, which proceeds at -60 °С, the protonation of imine nitrogen
occurs and intermediate iminium salts are formed – О,О-dialkyldithiophosphates Nalkylchloroaldiminium (4). At the second step, which is observable at -5-0 °С, the chlorine atom is
substituted by О,О-dialkyldithiophosphate group. The final products of the reaction are chlorides of
N-alkyl-2-О,О-dialkyldithiophosphatopropaniminium (5). We propose that salt (4) is transfromed
into product (5) through the intermediacy of salt (6) with delocalized azaallyl dication as a result of
heterolytic dissociation of the bond tertiary carbon-chlorine.
Synthetic result of the reaction of dithioacid (3) with N-alkyl-2-bromoaldimine (2) is completely
different – as major products were obtained phosphorylsulfide (7) and iminium salt of unsubstituted
aldimine (8). Thus, we for the first time discovered the reaction of reduction of organic bromine
derivative (2) by О,О-dialkyldithiophosphoric acid. At temperatures -80 – -70 °С, 31Р NMR
spectroscopy allowed to detect the formation of intermediate salt (9, δ 108 ppm).
The work is supported by RFBR and the Government of Tatarstan, project №13-03-7098_p
povolzhe _а/2013 and Ministry of education and Science (task № 2014/56 within the framework
of basic part of stat task).
115
P5
METAL-FREE TRANSANNULATION REACTION OF INDOLES WITH
NITROSTYRENES: SIMPLE PRACTICAL SYNTHESIS OF QUINOLINE
DERIVATIVES
A.V. Aksenov1, N.A. Aksenov1, I.V. Aksenova1, A.N. Smirnov1, M. Rubin2
1 - Department of Chemistry, North Caucasus Federal University, Stavropol, Russian Federation
2 - Department of Chemistry, University of Kansas,Lawrence, USA
A convenient metal-free method for preparation of a large variety of 3-aryl- and 3-alkylsubstituted
2-quinolones 4, as well as 2,3-disubstituted quinolines, was proposed. This approach involves
previously unknown transannulation of 2-substituted indoles 1 in the reaction of β-nitrostyrenes 2 in
polyphosphoric acid. The method is based on the ring-expansion of the pyrrole cycle in indoles
upon attack of amphyphilic reagents at the enamine double bond.
R
+
N
1
R
2
R
R
R
3
N
1
R
O
N
O
R
O P ( O )( O H ) 2
3
PPA
+
-H
2
N
N
R
+
R
H2O
O
2
R
+
R
+ H
R
3
R
2
N
1
+
3
R
OH
OH
OH
N
O P ( O )( O H ) 2
3
H
N
3
1
O P ( O )( O H ) 2
3
O P ( O )( O H ) 2
O P ( O )( O H ) 2
NH
2
N
R
1
R
1
2
O
N
N
R
1
R
2
NH
O
R
1
R
N
R
O
3
2
O
HO
R
HN
R2
3
R
3
O
+
N
O P ( O )( O H ) 2
4
R
O
N
1
R
1
N
H
O
P
O
H
R
+
N
R
P
O
O
+
O
3
2
R
N
P
OH
OH
N
OH
NH
O
1
R
O
2
R
R
3
R
2
O
1
R1= H, Me; R2= Ph, Me; R3= Ph, 4-MeOC6H4, 4-iPr-C6H4, 3,4-Me2C6H3, 4-EtOC6H4,2-FC6H4, 3,4Cl2C6H3, 3-BrC6H4, n-Pr
Introduction of an alkyl substituent into β-position of β-nitrostyrene 6 renders formation of
quinoline 7 as major product. The mechanism of this transformation is identical to the one shown
above, but includes elimination of water and aromatization at the last step.
3
3
2
R
1
+
R
+
N
N
H
R
O
N
O
6
7
2
O
+
3
2
H2N
R
5
R = Ph, Me; R = Ph, Ph.
Convenient and general metal-free approaches to 3-aryl and 3-alkyl-substituted 2-quinolones, as
well as to 2,3-disubstituted quinolines were developed, which included the previously unknown
process of transannulation of 2-substituted indoles in the reaction with β-nitrostyrenes in
polyphosphoric acid. The reaction was also efficiently combined into a cascade with a Fisher indole
synthesis. Unlike most other known methods, the described protocol utilizes readily available
starting materials. Unique properties of PPA, serving as a mild proton donor, source of efficient
leaving group (or temporary protecting group), water scavenger and high boiling solvent makes it
an ideal media for the described transformation.
This work was carried out with financial support from the RFBR (grant 13-03-003004)
116
P6
MECHANOCHEMICAL SYNTHESIS OF CHROMIUM CARBOXYLATES
AND THEIR CATALYTIC PROPERTIES IN ETHYLENE TRIMERIZATION
K.A. Alferov1, L.A. Petrova2, V.D. Makhaev2, G.P. Belov1
1 - Institute of Problems of Chemical Physics RAS, Department of Polymers and Composite
Materials, Chernogolovka, Russian Federation
2 - Institute of Problems of Chemical Physics RAS, Department of Functional Inorganic Materials,
Chernogolovka, Russian Federation
Selective synthesis of individual alpha olefins (1-butene, 1-hexene, 1-octene) is an urgent problem
because these compounds are widely used for the production of ethylene copolymers, plasticizers,
lubricants, etc. [1, 2]. One of the most efficient systems for ethylene trimerization is a system based
on chromium tris(2-ethylhexanoate) (Cr(EH)3), 2,5-dimethylpyrrole and organoaluminum
compounds. Methods for the synthesis of Cr(EH)3 based on reactions in solutions are quite
laborious and lingering. The products obtained by the methods are sticky and unhandy. The
operations for the isolation and purification of the product complicate its production [3, 4, 5].
Nowadays, green chemistry seems as a very promising research area, so the processes of solventfree solid reactant interactions attract much attention. We have developed a method for the
synthesis of Cr(EH)3 based on the solvent-free mechanochemical interaction of solid CrCl3 and
NaEH with subsequent heating of the reaction mixture [6]. Physicochemical properties of the
reaction products and mechanically activated CrCl3-NaEH mixtures at different CrCl3/NaEH ratios
were investigated by IR-spectroscopy, XRDA and DCS. The solid phase interaction of CrCl3 and
NaEH occurs in two main stages: 1) the reagents mixture mechanical activation resulting in their
dispersion and mixing at the molecular or cluster level; and 2) thermally initiated exothermic
interaction of the activated reactants to give the final products. The use of the method makes it
possible to shorten the process duration appreciably.
The obtained reaction mixtures and isolated Cr(EH)3 as well as commercially available Cr(EH)3 (810 % wt. in mineral spirits) were tested as components of the Cr(EH)3/2,5dimethylpyrrole/AlEt3/CCl4 catalytic system for ethylene trimerization. The productivity and
selectivity of the catalyst based on Cr(EH)3 synthesized by the mechanochemical method were
similar to the results obtained for the commercial Cr(EH)3. Moreover, reaction mixtures produced
directly after the synthesis of Cr(EH)3 also form an active catalyst for ethylene trimerization.
Syntheses differed in the time of mechanochemical activation (1-4 h) and reagent ratio
(NaEH/CrCl3 = 2.3 – 3.9) were also performed. The catalytic systems based on thus obtained
reaction mixtures demonstrated close values of productivity (11-13 kg/(gCr·h)) and selectivity (1-С6
= 82-85 % wt., C8+ = 13-15 % wt., PE = 0,1-0,3 % wt.) in ethylene to 1-hexene trimerization.
The study was in part financially supported by the Russian Foundation for Basic Research (project
no. 12-03-00974-a) and by the Presidium of the Russian Academy of Sciences Basic research
Program № 3.
[1] Dixon J.T., Green M.J., Hess F.M., Morgan D.H. J. Organomet. Chem. 689(23) 3641-3668
(2004).
[2] McGuinness D. S. Chem. Rev. 111(3) 2321-2341 (2011).
[3] Briggs J.R. US 466838 (Union Carbide Corporation), March 14, 1986.
[4] Knudsen R.D. et al. US 2007/0043181 A1 (Chevron Phillips Chemical Company), August 19, 2005.
[5] Sydora O.L. et al. US 2013/0150642 A1 (Chevron Phillips Chemical Company), December 12,
2011.
[6] Rus. Patent Application 2013156512/20(088111) (IPCP RAS), December 20, 2013.
117
P7
EFFECT OF CHEMICAL STRUCTURE OF VIOLOGEN-DERIVATIVES AS
AN ARTIFICIAL CO-ENZYME ON THE CARBON DIOXIDE REDUCTION
ACTIVITY OF FORMATE DEHYDROGENASE
Y. Amao1, S. Ikeyama2
1 - Osaka City University,Advanced Research Institute for Natural Science and Technology,
Osaka,Japan
2 - Osaka City University,Graduate School of Science, Osaka,Japan
Many studies on electro-catalyzed CO2 reduction have been performed using specific electrode
materials. On the other hand, studies on CO2 fixation also have investigated photocatalysis on
semiconductors such as titanium dioxide, silicon carbide and strontium titanate. However, these
systems use ultraviolet irradiation and the total reaction is low yield, whereas highly efficient CO2
fixation system using visible light is more desirable. We previously reported a system for visible
light-induced methanol synthesis from CO2 with the system formate, aldehyde, and alcohol
dehydrogenases, and methylviologen (MV2+) photoreduction by the visible light photosensitization
of water soluble zinc porphyrin in the presence of an electron donor in aqueous media. On this
system, the reduced form of methylviologen (MV.+) is used as an artificial co-enzyme for these
dehydrogenases. To improve the yield for methanol production from CO 2, conversion of CO2 to
formic acid with formate dehydrogenase (FDH) and reduced formed viologen is most important
step.
In this work, some artificial co-enzymes with 4,4’- bipyridine skeletons as shown in Figure 1 are
synthesized and effect of chemical structures of
artificial co-enzymes on the activity of the reduction
of CO2 to formic acid with FDH are investigated.
The conversion of CO2 to formic acid with FDH and
one-electron reduced form of artificial co-enzyme
was carried out as following method. The sample
solution containing 3.0 µmol of artificial co-enzyme,
5.7 mmol of sodium dithionate, and FDH (10 units)
in 3.6 ml of CO2 saturated sodium pyrophosphate Figure 1. Chemical structures of viologen-derivatives as
buffer (pH 7.4) at 30.5 ˚C for 1 min. The formic acid artificial co-enzymes for formate dehydrogenase
concentration produced is measured by ionic chromatography.
By using MV2+ as the reference, the formic acid production increased by using cationic artificial coenzymes (H2NH2CH2C-V-CH2CH2NH2 and CH3-V-CH2CH2NH2). On the other hand, the HCOOH
production decreased by using anionic co-enzymes (HOOCH2C-V-CH2COOH and CH3-VCH2COOH). The production of formic acid in this reaction depends on chemical structures of
artificial co-enzymes. Among the artificial co-enzymes, H2NH2CH2C-V-CH2CH2NH2 has high
affinity for FDH compared with the other compounds.
118
P8
Cu(I)-CATALYZED ARYLATION OF BIOLOGICALLY ACTIVE
DI- AND POLYAMINES
A.D. Averin, M.V. Anokhin, S.P. Panchenko, I.P. Beletskaya
M.V. Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
Di- and polyamines like putrescine, cadaverine, spermidine and spermine were chosen for the
studies of their Cu(I)-catalyzed N,N’-diarylation for the synthesis of new compounds with diverse
biological activity. Arylation was carried out using iodobenzene, 4-fluoroiodobenzene, 4(trifluoromethyl)iodobenzene and 4-iodobiphenyl. The reactions of butane-1,4-diamine were
successfully catalyzed with either CuI/L1 (L1 = L-proline) or CuI/L2 (L2 = 2isobutyrylcyclohexanone) systems while pentane-1,5-diamine demonstrated better results with
CuI/L2 system. Cs2CO3 was taken as a base in all cases.
Selective N1,N3-diarylation of triamine and N1,N4-diarylation of tetraamine turned to be a more
complicated task, and target compounds were obtained in moderate yields using CuI/L2 catalytic
system.
Acknowledgement: The work was financially supported by the RFBR grant N 12-03-00796.
119
P9
NITRATING AND NITROSATING REAGENTS IN NOVEL
HETEROCYCLIZATION REACTIONS. READY ACCESS TO HIGHLY
SUBSTITUTED PYRIMIDINE AND ISOXAZOLE DERIVATIVES
E.B. Averina, K.N. Sedenkova, D.A. Vasilenko, T.S. Kuznetsova, N.S. Zefirov
Lomonosov Moscow State University, Department of Chemistry
Recently we have elaborated novel synthetic approaches to five- and six-membered N- and N,Oheterocycles basing on the heterocyclization of electrophilic alkenes or three-membered carbocycles
under the treatment with nitrating or nitrosating reagents.
The reaction of tetranitromethane with electrophilic alkenes in presence of triethylamine was found
to afford 5-nitroisoxazoles 1 – highly reactive and versatile compounds which may be used as
precursors of diverse functionalized compounds [1]. Employing the reduction of nitroisoxazoles 2
we suggested the regioselective method of synthesis of 5-aminoisoxazoles 2 that was used to
accomplish a structure design of biologically active compounds. The series of compounds 2 was
obtained in good yields (50-90%) and their antiviral activity was investigated.
A series of previously unknown 4-fluoropyrimidine 1-oxides 4 was obtained via three-component
heterocyclization involving gem-bromofluorocyclopropanes 3, nitrosating or nitrating agent and
organic nitrile [2]. Preparative method of synthesis of 4-fluoropyrimidines 5 from corresponding Noxides under the treatment with PCl3 was elaborated.
F
R2
EWG
N
1
O
C(NO2)4 -Et3N
NO2
SnCl2 EtOH
R2
EWG
N
O
2
:CBrF
R1
R2
R1 = EWG (C(O)R',
CO2R", P(O)(OEt)2
NO2, CO2R");
R2 = H, Alk
R1
R2
F
[NO+]
Br RCN R2
3
R,R1,R2: Alk, Ar;
[NO+]: NOBF4,
NO2BF4, NO2OTf
NH2
R1
N
N
4 O
R
PCl3
F
R1
R2
N
N
5
R
4-Fluorosubstituted pyrimidine N-oxides 4 and pyrimidines 5 demonstrate high reactivity in
aromatic nucleophilic substitution with various O-, N-, P-nucleophiles. In particular, a series of 4aminopyrimidines and pyrimidine N-oxides, potent as compounds with antiviral activity, was
obtained via this reaction.
In conclusion, simple and efficient synthetic methods allowing polyfunctionalized isoxazoles,
pyrimidines and pyrimidine N-oxides, including those with valuable properties, from readily
available starting materials were developed.
We thank the Russian Foundation for Basic Research (Projects 14-03-31989-mol_а, 14-03-00469a) and Presidium RAS (program №8P) for financial support of this work.
[1] (a) Y.A. Volkova, E.B. Averina, Y.K. Grishin, P. Bruheim, T.S. Kuznetsova, N.S. Zefirov J. Org. Chem.,
2010, 75, 3047-3052; (b) E.B. Averina, Y.A. Volkova, Y.V. Samoilichenko, Y.K. Grishin, V.B.
Rybakov, A.G. Kutateladze, M.E. Elyashberg, T.S. Kuznetsova, N.S. Zefirov Tetrahedron Lett., 2012,
53, 1472–1475. [2] (a) K.N. Sedenkova, E.B. Averina, Yu.K. Grishin, A.G. Kutateladze, V.B. Rybakov,
T.S. Kuznetsova, N.S. Zefirov J. Org. Chem., 2012, 77, 9893–9899; (b) K.N. Sedenkova, E.B. Averina,
Yu.K. Grishin, T.S. Kuznetsova, N.S. Zefirov Tetrahedron Lett., 2014, 55, 483–485.
120
P10
TRANSFER HYDROGENATION OF ACETOPHENONE OVER BIS-IMINE
RHODIUM(I) COMPLEX. DFT STUDY
N.M. Badyrova1, Z. Lin2, L.O. Nindakova1
1 - Irkutsk State Technical University, Physical and Technical Institute, Irkutsk, Russia
2 - The Hong Kong University of Science and Technology, Department of Chemistry, Hong Kong
(P. R. China)
There are two reaction mechanisms for asymmetric transfer hydrogenation reactions of ketones over
a diamine rhodium(I) complex leading to optically active secondary alcohols: a stepwise process
through an intermediate hydride complex derived from an alkoxy complex via -hydride
elimination and a concerted process where the hydrogen is directly transferred from the alkoxy
complex to the coordinated substrate [1].
Here, we investigated mechanism of hydrogen transfer reaction (Scheme 1) from 2-propanol to
acetophenone over a bis-imine-rhodium(I)-chloride complex with optical active bis–imine ligand
R,R-1 on the basis of DFT theoretical calculations.
Scheme 1
Based on the mechanism proposed by Guiral et al [1], we designed a catalytic cycle (Scheme 2).
This cycle starts with the hydride complex 1. The first step is reversible dissociation of a Rh-N
bond in the 18-electron hydride complex leading to a 16-electron intermediate (the hydride complex
2). From 2, there are two possible pathways to achieve hydride transfer to acetophenone, an external
pathway vial 3a and an internal pathway via 3b (Scheme 2). Both the two hydride transfer pathways
give the alkoxy complex 4, which leads to 5 after with a metathesis with 2-propanol to release the
product molecule. Next step involves -H elimination to give 6 followed by release of the sideproduct (acetone) to regenerate the starting hydride complex 1.
H3 C
N
N
N
N
H
Rh
Rh
N
N
N
H
3a
N
N
1
N
N
Scheme 2
H
H3 C
C
O
Rh
N
CH3
N
N
N
6
CH
N
N
N
4
Ph
N
Ph
(CH3)2CHOH
N
H3C
CH
Rh
Rh
O
H
N
3b
(CH3)2CO
C
Rh
N
H3C
O
N
CH3
O
N
Rh
H
N
2
N
Ph
C
O
N
CH3
(CH3)PhCHOH
N
5
Geometry optimizations of all species have been performed by means of the DFT M06 hybrid
method [2]. The 6-31G(d) basis set was chosen to describe C, N, O, H atoms and the LanL2DZ
basis set was used for Rh. All of the calculations were performed with the Gaussian 09 program [3].
1. Guiral V., Delbecq F., Sautet P. Organometallics, 2000, 19, 1589-1598.
2. Zhao Y., Truhlar D. G., Theor Chem Account, 2008, 120, 215-241.
3. Frisch, M. J.; et al. Gaussian 09, Revision A.1; Gaussian Inc., Wallingford, CT, 2009.
121
P11
RHODIUM(II) CATALYZED REACTIONS FOR SYNTHESIS OF NOVEL
AND DIVERSE FURO[2,3-D]PYRIMIDINEDIONES AND
THIOXOFURO[2,3-D]PYRIMIDINEONES
E.R. Baral, K.B. Somai Magar, Y.R. Lee
School of Chemical Engineering, Yeungnam University, Gyeongsan 712-749, Republic of Korea
Furopyrimidines, the derivatives of pyrimidine and analog of purine have been demonstrated to
have antimalarial, antifolate, antitumor, antiviral, antibacterial and antifungal, and antihypertensive
properties.1-2 Accordingly, several methods have been devised to synthesize furopyrimidines.3-4 The
general methods for the synthesis of furo[2,3-d]pyrimidinediones by ceric ammonium nitrate
mediation involving ionic (non-carbenoid) mechanism is limited with the substrate scope in terms
of olefins and alkynes with low yields,5 while three component reactions of N,N’-dimethylbarbituric
acid with benzaldehydes, and isocyanides, provided 2,3-disubstituted furans.6 However, there is a
need for more convenient and efficient synthetic methods for the preparation of furo[2,3d]pyrimidinedione derivatives, and in particular, the synthesis of thioxofuro[2,3-d]pyrimidinedione
derivatives has not been reported to date.
In this conference, we present the rhodium (II)-catalyzed reactions of cyclic diazo compounds
derived from barbituric acid or thiobarbituric acid with arylacetylenes and styrenes. These reactions
provide a rapid synthetic route to the preparation of a variety of novel and diverse furo[2,3d]pyrimidine-2,4-diones,
2-thioxodihydrofuro[2,3-d]pyrimidin-4-ones,
dihydrofuro[2,3d]pyrimidine-2,4-diones, and 2-thioxotetrahydrofuro[2,3-d]pyrimidin-4-ones.
O
O
R
X
R
Y'
N
N
R
O
Y'
X
Rh 2(OPiv) 4
toluene
reflux
N2
N
N
R
O
X=O, S
R=Me, Et
O
Y
Rh2(OPiv)4
PhF
rt - 60 oC
R
X
N
N
R
O
Y
References
1. G. Jähne, H. Kroha, A. Müller, M. Helsberg, I. Winkler, G. Gross, T. Scholl, Angew. Chem. Int.
Ed. Engl. 1994, 33, 562-563.
2. Q. Dang, Y. Liu, M. D. Erion, J. Am. Chem. Soc. 1999, 121, 5833-5834.
3. A. Sniady, M. D. Sevilla, S. Meneni, T. Lis, S. Szafert, D. Khanduri, J. M. Finke, R. Dembinski,
Chem. Eur. J. 2009, 15, 7569-7577.
4. A. Sniady, A. Durham, M. S. Morreale, A. Marcinek, S. Szafert, T. Lis, K. R. Brzezinska, T.
Iwasaki, T. Ohshima, K. Mashima, R. Dembinski, J. Org.Chem. 2008, 73, 5881-5889.
5. K. Kobayashi, H. Tanaka, K. Tanaka, K. Yoneda, Synth. Commun. 2000, 30, 4277-4291.
6. M. B. Teimouri, R. Bazhrang , Bioorg. Med. Chem. Lett. 2006, 16, 3697-3701.
122
P12
DUAL REACTIVITY OF NTROARENES IN [4+2]-CYCLOADDITION
REACTIONS
M.A. Bastrakov, A.M. Starosotnikov, S.A. Shevelev
N.D. Zelinsky Institute of Organic Chemistry RAS, Laboratory of Nitrogen-containing Aromatic
Compounds, Moscow, Russia
[4+2]-Cycloaddition is one of the fundamental protocols for the construction of a new ring, which
accompanies the formation of two bonds. This reaction is known for nitroalkenes1a, as well as for
few highly electrophilic (low aromatic) benzoazoles1b-c. These compounds readily undergo DielsAlder reactions at C-C double bond activated by the nitro group. Also they form anionic σ-adducts
with very weak nucleophiles1b.
As a part of our research on highly electrophilic heterocyclic systems we have found that 4,6dinitroanthranil reacts with dienes and nucleophilic dienophiles in mild conditions2.
Moreover we have proposed methods for the synthesis of new policyclic heteroaromatic
compounds on the nitroarenes basis consisting in annelation of a furoxan ring to different
dinitrobenzoazoles and azines3. Some of these compounds readily undergo [4+2]-cycloaddtition
with dienes and dienophiles.
This work was supported by the Russian Foundation for Basic Research, Projects No. 13-03-00452,
14-03-31508 mol_a and Grant of the President of the Russian Federation for State Support to young
Russian scientists, Grant MK-3599.2013.3.
1. (a) S.E. Denmark, A. Thorarensen, Chem Rev., 1996, 96, 137; (b) S. Lakhdar, R. Goumont, T.
Boubaker, M. Mokhtari, F. Terrier, Org. Biomol. Chem., 2006, 4, 1910; (c) S. Kurbatov, R.
Goumont, S. Lakhdar, J. Marrot, F. Terrier, Tetrahedron, 2005, 61, 8167;
2. A.M. Starosotnikov, M.A. Leontieva, M.A. Bastrakov, A.V. Puchnin, V.V. Kachala, I.V.
Glukhov, S.A. Shevelev, Mendeleev Commun, 2010, 20, 165.
3. M.A. Bastrakov, A.M. Starosotnikov, I.V. Glukhov, S.A. Shevelev, Russ. Chem. Bull. Int. Ed.,
2009, 58, 426.
123
P13
UNEXPECTED FORMATION OF N-ALKYLIMIDES IN REACTION OF
MALEOPIMARIC AND CITRACONOPIMARIC ACIDS WITH
SECONDARY AMINES
M.P. Bei1, A.P. Yuvchenko1, A.V. Baranovsky2
1 - The Institute of Chemistry of New Materials, 36 F.Skoriny st., Minsk 220141, Belarus
2 - The Institute of Bioorganic Chemistry, 5/2 Kuprevich st., Minsk 220141, Belarus
The Diels-Alder reaction of levopimaric acid with active dienophiles produces adducts (maleo-, fumaro-,
quinopimaric acids) which are useful precursors in the synthesis of chiral ligands, terpenoquinones,
biologically active compounds. Recently, we have reported the synthesis of isomer of citraconopimaric acid
(2), an analog of well-known maleopimaric acid (1), bearing methyl group at C-15.1 The method includes
preparation of the adduct of pine rosin with citraconic anhydride (formed in situ from itaconic acid) followed
by recrystallization of the product from carbon tetrachloride and benzene.
We have initiated the investigation of the reaction of citraconopimaric acid (2) with some secondary aliphatic
amines in order to study the steric influence of the CH3 group at C-15 of the acid (2) on regioselectivity of
anhydride ring opening by nucleophilic agents.
It was established that the heating of citraconopimaric acid (2) solution in diethylamine, dipropylamine in
autoclave, dibutylamine at 135ºC for 30h leads to the formation of N-ethyl-, N-propyl-, N-butylimides of
citraconopimaric acid (3−5). Unlike citraconopimaric acid (2), reactions of maleopimaric acid (1) with
diethyl-, dipropylamine at 135ºC gave N-ethyl-, N-propylimides of maleopimaric acid (6, 7; yields 60−80%)
and amidodiacids (9, 10; yields 10−15%), and the reaction with dibutylamine gave only maleopimaric acid
N-butylimide (8).2
O
R' = CH3
O
O
R' O
o
+ R2NH
135 C
NR
O
COOH (3, 4, 5)
R = C2H5 (3), n-C3H7 (4), n-C4H9 (5)
O
COOH
R' = H (1), CH3 (2)
NR
O +
R' = H
COOH (6-8)
COOH
NR2
O
*
COOH (9, 10)
R = C2H5 (6, 9), n-C3H7 (7, 10), n-C4H9 (8)
* The exact structure of regioisomer is not established
The formation of N-alkylimides (3−8) in the above transformations could be result of a thermal degradation
of intermediate amidoacids giving stable cyclic imides. Would this assumption be true, the formation of
mixture of two imides should be observed in the reaction of acids (1, 2) with unsymmetrical secondary
amines. Thus, when acids (1, 2) were treated with methyl- or ethyl-(2-hydroxyethyl)amine, the formation of
a mixture of two imides indeed was observed.2
O
(1, 2) +
R
H
N
O
NR
135oC
R' O
OH
+
N
R' O
OH
COOH
COOH
R = CH3, C2H5, R' = H, CH3
[1] M.P. Bei, A.P. Yuvchenko. Patent of the Republic of Belarus 13,646, 2009.
[2] M.P. Bei, A.P. Yuvchenko, A.V. Baranovsky. Proceed. Nat. Acad. Sci. Belarus. 2013, N 4, 104
124
P14
SYNTHESIS OF TRYPTAMINES FROM CYCLOPROPYLKETONES
ARYLHYDRAZONES AND THEIR BIOLOGICAL STUDIES
A.Yu. Belyy1, R.F. Salikov2, Yu.V. Tomilov2
1 - Higher Chemical College of Russian Academy of Sciences
2 - N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
Tryptamine derivatives are psychoactive compounds and are widely used as 5-HT agonists. We
have found that cyclopropyl methyl ketone hydrazones rearrange into a mixture of
tetrahydropyridazines and tryptamines, the best yield of tryptamine being observed in the case of
generated in situ bromophenylhydrazone. The rearrangement of cyclopropyl ketones with a bulky
group in most cases gives tetrahydropyridazines exclusively.
The tryptamine derivatives obtained demonstrated their antitumor activity against human
neuroblastoma cell line SH-SY5Y. The best result was shown by 2-methyl-5-bromotryptamine
(IC50 = 5,06 µМ) with the therapeutic index of 4, determined from the toxicity against human
embryonic kidney cells (HEK 293).
In order to investigate the biological activity of this interesting class of compounds we derived the
tryptamines in three different ways: substitution of bromine, indole nitrogen alkylation and primary
amine nitrogen. The biological studies are under performance.
125
P15
DEHYDROGENATION OF LOW ALIPHATIC ALCOHOLS ON COPPER
SUPPORTED STRUCTURED CATALYST
D.A. Bokarev1, E.A. Ponomareva2, E.V. Egorova2
1 - N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia
2 - Lomonosov Moscow State University of Fine Chemical Technologies, Moscow, Russia
The important direction of the chemical industry development is engineering of new alternative
manufactures based on renewable sources of raw materials. These materials could be methanol and
ethanol, especially applied for synthesis of methylformiat and acetaldehyde respectively.
2CH3OH → HCOOCH3+2H2
C2H5OH → CH3CHO +H2
To realize the process of dehydrogenation with high technical parameters new catalytic systems
must be worked out. Recently new classes of heterogeneous catalysts based on structured carbon
fibers were developed. They possess a number of advantages - homogeneous distribution of a
stream, low pressure drop. Moreover, fibers structured catalysts offer flexibility and endless forms
that allow using them in reactors of a various constructions.
It was shown that 5 wt.% of copper supported by impregnation appeared to be optimal in the
process of alcohol dehydrogenation. Compared to powder and granular carbon materials used
earlier, catalysts based on structural carbon fibers showed higher activity and selectivity due to
better distribution of active component on the surface of the carrier (fig.1).
Activity – 126 gMeOH/gCu*h and 237 gEtOH/gCu*h
Activity – 24 gMeOH/gCu*h and 68 gEtOH/gCu*h
Fig. 1. Distribution of copper particles on the surface of carbon structured fiber (left) and granular
carbon material Sibunit (right)
Thus, application of structured carbon fibers as a support of copper catalytic system leads to
increase of activity in comparison with known literature data. That allows to make a conclusion
about appropriateness of using it in the process of dehydrogenation of low aliphatic alcohols.
126
P16
ARYLAMINATION OF 1,3,7-TRIAZAPYRENES
I.V. Borovlev, O.P. Demidov, N.A. Saigakova, G.A. Amangasieva
North Caucasus Federal University, Department of Chemistry, Stavropol, Russia
In our previous reports we have shown that 1,3,7-triazapyrene displays peculiar properties due to
the unique fusion of the carbocyclic and heterocyclic rings. Specifically these properties include the
unusual ease of oxidative nucleophilic substitution of hydrogen, such as amination [1] and
alkylamination [2], which proceed in aqueous media. The aim of this work is the synthesis of
arylamino derivatives of this heterocycle. In spite of a common mechanism, the conditions
mentioned above are not suitable for arylamination reaction due to the low nucleophilicity of aryl
amines and their high sensitivity towards oxidation. This is why SNH-arylamination reactions are
still rare.
We have found that the interaction of 1,3,7-triazapyrenes 1 with an excess of sodium arylamides
obtained in situ in absolute DMSO proceeds at room temperature to form the 6-aryl(hetaryl)amino1,3,7-triazapyrenes 2 in 32-97 % yields. It was shown that the decisive factor for rearomatization of
σH-adducts is crucial access to the air oxygen.
R
R
N
N
N
N
1 . A rN H - N a +
DM SO, RT, O2
2 . H 2O
X
X
N
N
N H Ar
2
1
R = H, Me; X = H, Ar, NR2
Under the same conditions (DMSO, room temperature) the reaction of the rather accessible 6,8dialkoxy-1,3,7-triazapyrenes 3 with sodium aryl amide has resulted to a product of nucleophilic
ipso substitution of one of the two RO groups - 6-alkoxy-8-aryl(hetaryl)amino-1,3,7-triazapyrenes
4.
N
N
N
N
1 . A rN H - N a +
1 . A rN H - N a +
re flu x in g to lu e n e
DM SO, RT
2 . H 2O
2 . H 2O
RO
N
4
N H Ar
N
N
RO
N
3
OR
ArN H
N
N H Ar
5
R = Me, Et
Products of double ipso substitution – 6,8-bis(aryl(hetaryl)amino)-1,3,7-triazapyrenes 5 were
synthesized by refluxing of the compounds 3 with excess of the sodium arylamides in toluene for a
long time. Consecutively replacing one methoxy group in 6,8-dimethoxy-1,3,7-triazapyrene in
DMSO, and the second - in toluene, we obtained asymmetrically substituted diamine - 6phenylamino-8-(pyridin-4-ylamino)-1,3,7-triazapyrene.
This project received financial support from the Ministry of Education and Science of the Russian
Federation in the framework of the State Assignment to the Higher Education Institutions №
4.141.2014/K.
[1]. O. P. Demidov, I. V. Borovlev, N. A. Saigakova, O. A. Nemykina, N. V. Demidova, and S. V.
Pisarenko, Khim. Geterotsikl. Soedin., 142 (2011). [Chem. Heterocycl. Compd., 47, 114 (2011).]
[2]. I. V. Borovlev, O. P. Demidov, N. A. Saigakova, S. V. Pisarenko, O. A. Nemykina, J.
Heterocycl. Chem., 48, No. 5, 1206 (2011).
127
P17
SUSTAINABLE APPROACHES FOR ORGANIC SYNTHETIC PROCESSES
L.C. Branco, K. Zalewska, G. Carrera, M.N. Da Ponte
REQUIMTE, Departamento de Quнmica, Faculdade de Ciкncias e Tecnologia, Universidade Nova
de Lisboa, 2829-516 Caparica, Portugal
For many synthetic approaches the incorporation of CO2 as alternative reagent or green solvent can
improve significantly the efficiency (yields, purity, reaction conditions) for several organic
processes. In recent years, the use and capture of Carbon Dioxide (CO2) became a hot research topic
including their application for organic and pharmaceutical chemistry.1 The possibility to use carbon
dioxide as useful reagent for different synthetic approaches or supercritical CO2 for efficient
extraction and separation processes has been reported.1
The combination of ionic liquids and supercritical fluids has been reported for many organic
transformations in particular catalytic reactions.2 The possibility to use scCO2 in order to extract the
pure products without IL or catalyst contamination is one of the advantages for these processes.
Several publications proof the advantages for ILs and scCO2 combinations in order to recycle the
catalytic media during many reaction cycles without loss of efficiency.
In this communication, we described the applicability of carbon dioxide approaches in two different
organic synthetic processes:3
a) The use of CO2 as reagent for the preparation of reversible chiral and non-chiral carbamate
salts by the reaction with different amines (e.g. primary alkyl and aryl amines or polyamines),
aminoacids and pharmaceutical compounds in the presence of an organic superbase (e.g. DBU or
tetramethylguanidine). According with the optimized reaction conditions, it´s possible to tune the
chemical and thermal stability as well as potential application of the final salts.
b) The potential use of scCO2 for extraction and separation processes in the case of three
asymmetric catalytic reactions in the presence of ionic liquids and/or chiral ionic liquids as
solvent or chiral media respectively. In particular, Sharpless asymmetric dihydroxylation of olefins
(in the presence of osmium catalyst), asymmetric Aldol and Michael reactions (in the presence of
chiral organocatalysts based on chiral ILs) will be presented.
The peculiar properties of carbon dioxide including as supercritical fluid open excellent
perspectives for the application in novel organic synthetic transformations as well as their use in
industrial processes.
Acknowledgements: We thank the Fundação para a Ciência e Tecnologia for financial support
(PEst-C/EQB/LA0006/2011 and PTDC/CTM/103664/2008 projects and SFRH/BD/67174/2009 for
KZ PhD grant).
References:
1. a) Goodrich, B. F.; de la Fuente, J. C.; Gurkan, B. E.; Zadigian, D. J.; Price, E. A.; Huang, Y;
Ind. Eng. Chem. Res. 2011, 50, 111. b) Camper, D.; Bara, J. E.; Gin, D. L.; Noble, R. D.; Ind.
Eng. Chem. Res. 2008, 47, 8496.
2. Afonso, C. A. M.; Branco, L. C.; Candeias, N. R.; Gois, P. M. P.; Lourenço, N. M. T.; Mateus,
N. M. M.; Rosa, J. N.; Chem. Commun. 2007, 2669.
3. a) Carrera, G. V. M.; da Ponte, M. N.; Branco, L. C.; Tetrahedron, 2012, 68, 7408. b) Branco, L.
C.; Serbanovic, A.; da Ponte, M. N.; Afonso, C. A. M.; ACS Catalysis 2011, 1, 1408. c) Carrera,
G. V. S.M.; Costa, A.; Ponte, M. N.; Branco, L.C., Synlett 2013, 24, 2525.
128
P18
1
H AND 13C ASSIGNMENTS OF THREE SERIES BIOACTIVE
IMIDAZO[2,1-B]THIAZOLE DERIVATIVES
A.S. Bunev, E.V. Sukhonosova, G.I. Ostapenko, P.P. Purygin
Togliatti State University, Togliatti, Russia
The complete 1H and 13C NMR assignments of three series bioactive imidazo[2,1-b]thiazoles were
achieved by combination of one and two-dimensional NMR experiments, and the NMR signals of
these compounds were analyzed and compared.
The authors are grateful to the Ministry of Education and Science of the Russian Federation (State
job No. 426)
129
P19
SYNTHESIS OF 1,4,5-TRISUBSTITUTED IMIDAZOLES CONTAINING
TRIFLUOROMETHYL GROUP
A.S. Bunev, M.A. Vasiliev, G.I. Ostapenko, V.E. Statsyuk
Togliatti State University, Togliatti, Russia
A new synthetic protocol for the synthesis of 1,4,5-trisubstituted imidazoles (2a-i) containing
trifluoromethyl group has been developed using van Leusen reaction, which incorporates twocomponent condensation reaction trifluoroacetimidoyl chlorides (1a-i) with tosylmethylisocyanide.
This protocol provides a novel and improved method for obtaining trifluoromethyl containing 1,4,5trisubstituted imidazoles in good yields.
The authors are grateful to the Ministry of Education and Science of the Russian Federation (State
job No. 426)
130
P20
THE QUANTUM-CHEMICAL STUDY OF THE KEY STEP OF THE
CYCLIZATION OF 4,11-DIMETHOXY-5,10-DIOXO-2- ANTHRA[2,3-B]FURAN-3-CARBOXYLATES
E.E. Bykov, A.S. Tikhomirov, A.E. Shchekotikhin, M.N. Preobrazhenskaya
Gause Institute of New Antibiotics RASM, Moscow, Russia
Highly active inhibitors of topoisomerase I, capable of blocking the growth of tumor cells with
activated mechanisms of multiple drug resistance, were discovered in the series of derivatives 4,11dihydroxy-5,10-dioxoanthra[2,3-b]furan-3-carboxylic acids [1]. Previously, a scheme of preparation
of 2-substituted derivatives of 4,11-dimethoxy-5,10-dioxoanthra[2,3-b]furan-3-carboxylic acids was
developed. However yields of anthrafurandiones by this method seriously depended on a substituent
in position 2 [2]. To understand this, a quantum-chemical estimations of the key step of the
intermolecular cyclization of the intermediate enol forms of ethyl 2-(3-bromo-1,4-dimethoxy-9,10dioxo-9,10-dihydroanthracene-2-yl)-3-hydroxypropanoates 1a-c to the corresponding anthra[2,3b]furan-5,10-diones 2a-c were carried out.
The quantum-chemical calculations by DFT method B3LYP/6-31+G(d) by means program package
Gaussian-09 [3] confirmed that the activation barriers (ΔE# ) of cyclization of enol form 1a-c
depend on the nature of the substituent R. The groups R that have different electronic properties
influence actively on the electron density of the internal nucleophile what is enolic oxygen atom
(see Table, QO and ΕHOMO). The calculated values of ΔE# correlate with the yield of the anthra[2,3b]furan-5,10-diones 2a-c [2]. Thus quantum-chemical evaluation of the key step of cyclization
confirmed that the electron-withdrawing substituents reduce the reactivity of enol intermediates 1ac in the cyclization to the corresponding anthra[2,3-b]furan-5,10-diones 2a-c.
Table. Parameters for the reaction of cyclization of anthra[2,3-b]furan-5,10-diones 2a-c.
Derivative
2a
2b
2c
R
-CH3
-Ph
-CF3
ΔE#, (kcal/mol)
21.84
22.7
25.86
ΕHOMO, (ev)
-2.01
-2.23
-2.45
QO
-0.687
-0.577
-0.567
The yield, % [2]
72
40
3
References
1. Shchekotikhin, A. E. et. al, Patent RU № 2412166 (2011).
2. Tikhomirov, A. S.; Shchekotikhin, A. E.Chem. Heterocycl. Compd. 2014, 50, 271.
3. http://www.gaussian.com
131
P21
MACROPOLYCYCLIC COMPOUNDS COMPRISING DIAZACROWN
ETHER MOIETIES AND FLUOROPHORE GROUPS
N.M. Chernichenko, A.D. Averin, I.P. Beletskaya
M.V. Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
Macrobicyclic compounds comprising structural fragments of diazacrown ethers and oxadiamines
were synthesized using Pd-catalyzed amination reactions using Pd(dba)2/BINAP system [1]. They
were further modified with various fluorophore substituents using catalytic and non-catalytic
approaches to create promising fluorescent chemosensors and molecular probes for metal cations.
Modification was carried out at N atoms of the cryptand and at C atoms of the benzyl spacer.
Macrotricycles and isomeric trismacrocycles were obtained via Pd-catalyzed macrocyclization
reactions of N,N’-bis(3,5-dibromobenzyl) diazacrown ether derivatives with oxadiamines using
either BINAP or RuPhos ligands and were further modified with dansyl fluorophores.
Acknowledgement: The work was financially supported by the RFBR grant N 12-03-93107.
[1] A.A. Yakushev, N.M. Chernichenko, M.V. Anokhin, A.D. Averin, A.K. Buryak, F. Denat, I.P.
Beletskaya. Molecules, 2014, 19, 940-965.
132
P22
SYNTHESIS OF 1Н-IMIDAZOLECARBOXAMIDES
I.V. Zavarzin, V.N. Yarovenko, S.L. Semenov, E.I. Chernoburova, M.M. Krayushkin
N. D. Zelinsky Institute of Organic Chemistry, Laboratory for Chemistry of Steroid Compounds,
Moscow, Russia
We earlier proposed the method for synthesis of 4,5-dihydro-1Н-imidazolecarboxamides (1) by the
reaction of chloroacetamides with aliphatic diamines in the presence of sulfur1,2 (Scheme 1)
O
O
Cl
H 2 N ( C H 2) n2 N H 2
N
RNH
RNH
1
N
H
( C H 2)
n
n = 1 ,2
Scheme 1
In this work we propose the method for the transformation of products 1 into 1Нimidazolecarboxamides 2. We found that the interaction of 1а-с with Ni/Al alloy in aqueous
methanol at 20оС results in the dehydrogenation of dihydroimidazole fragments to form imidazoles
2а-с.
N
H
N
N
N
O
N
H
Ni/ A l, K O H
H
M e O H/ H 2 O
R
N
O
H
R
1 a -c
2 a -c
R = 2 -F ; 3 -O M e ; 2 ,4 -M e
Scheme 2
References
1. V.N. Yarovenko, S.A. Kosarev, I.V. Zavarzin, M.M. Krayushkin, Russ. Chem. Bull. (Int. Ed.)
1999, No. 4, p. 753.
2. M.M. Krayushkin, V.N. Yarovenko, I.V. Zavarzin, Russ. Chem. Bull. (Int. Ed.) 2004, No. 3, p.
491.
133
P23
FEP/MD PROTOCOL TO MODEL SELECTIVITY OF KINASE
INHIBITORS
G.G. Chilov, O.V. Stroganov, F.N. Novikov, A.A. Zeifman, V.S. Stroylov, I.Yu Titov, I.V.
Svitanko
ND Zelinsky Institute of Organic Chemistry RAS
With over 500 different kinase enzymes encoded in a human genome and appreciation the role of
kinases as promising therapeutic targets, the selectivity profile of a kinase inhibitor is an important
indicator of its potential off-target effects including adverse effects, which sometimes might be
quite severe and even preclude application of a drug in clinical practice. One of the recent examples
of how the lack of selectivity of a kinase inhibitor drug may restrict its clinical application because
of abundant life-threatening adverse effects is presented by Ponatinib - a potent inhitor of Abl
kinase (primary therapeutic target) as well as over 40 off-target kinases. With the intent to
overcome adverse effcts of Ponatinib we designed a PF-114 molecule, which appeard to be
comparable to Ponatinib with respect to Abl suppression, but inhibited only 10 off-target kinases. In
order to rationalize enhanced selectivity we established a FEP/MD protocol in which for each
kinase Ponatinib molecule was transformed to PF-114 and the dG of such transition was recorded.
The modeled system consisted of a full atom kinase domain with inhibitor docked into ATP-bindin
site and immersed in a box of explicit solvent. FEP transition was split into 3 steps: decharging
initial molecule (Ponatinib), converting Van der Waals parameters to another molecule (PF-114)
and then charging the resulting molecule. Each transition was split in its turn into 10 windows, each
taking 2 ns of MD simulation. Totally 15 kinases were modeled for the selectivity of inhibition. It
appeared that calculated selecivities correlaeted with experimental data with R of 0,63. Structural
findings from FEP/MD simulations uncovered 2 factors contributing to the enhanced selectivity of
PF-114: its unfavorable (compared to Ponatinib) interaction with main chain carbonyl oxygen
present in the active site of BRAF, Src, ERBB4, FGFR1, VEGFR2, TRKC, TRKB; and
unfavorable interaction with water molecule in the active sites of BRAF, EPHA7, FGFR1, FLT1,
MAPK11, MAPK14 kinases. Current results suggests that full atomic FEP/MD modeling may be a
valuable instrument in the design of kinase inhibitors with improved selectivity.
134
P24
FEATURES OF NATURAL POLYSACCHARIDE BASED THIN FILMS
FORMATION
Y.V. Chudinova2, D.V. Kurek2
1 - M.V.Lomonosov Moscow State University, Moscow, Russia
2 - Centre «Bioengineering», RAS, Moscow, Russia
Natural polysaccharide based thin films are promising biomaterials for using in different fields of
science. Thin films were prepared by layer-by-layer (LbL) technique via alternately dipping the
substrate into polycation and polyanion solutions to form polyelectrolyte multilayers. During each
adsorption cycle one a monolayer is built up and the surface charge is reversed. This assembly
process allows obtaining films with desired characteristic. Layer-by-layer method offers several
advantages over other thin film deposition techniques, for example it is simple, rapid and
inexpensive.
Polyelectrolyte LbL films can be assembled from chitosan, pectin and other natural polymers.
Pectin is one of the basic components of plant cell wall. It has a complex structure and contained
linear and branched regions. Chitosan is produced by deacetylation of chitin, which is the structural
element in the exoskeleton of crustaceans and cell walls of fungi. Chitosan and pectin are
considered as some of the most attractive natural polyelectrolytes, because they are nontoxic,
biodegradable, and biocompatible polymers. Their oppositely charged surface permits to use them
for generating biocompatible surfaces via multilayer assembly.
The main characteristic of biofilms, such as surface topography, roughness, thickness, molecular
structure, adhesion forces were determined by atomic force microscopy (AFM).
Influence of polyelectrolyte type and number of layers on the film buildup were investigated. Pectin
covers mica surfaces very well and filling degree is nearly 100 %. Chitosan forms heterogeneous
structures on the mica surface with a lesser filling degree. Chitosan with different molecular weight
was studied. Results showed that in all cases were formed particles and aggregates.
Influence of substrate type and its possible modifications was considered. Surface topography,
height, roughness of the films which formed on the substrates with different properties were varied.
Further, effect of the concentration and the presence of other polysaccharide were observed. Pectinchitosan and chitosan-pectin coatings which formed via layer-by-layer technique had different
morphological characteristics.
The adhesion of the polyelectrolyte multilayer films has been investigated by contact mode of
AFM. Adhesion is the attraction forces between the AFM tip and the film surfaces by force-curves
mode [1]. Obtained data demonstrated relationship between adhesion forces and surfaces properties.
Understanding of the molecular structure and pathways of formation such thin films allows to
predict the characteristics and produce coating materials for use in various fields of biology and
medicine.
References:
1. Guo Y.-B., Wang D.-G, Adhesion and friction of nanoparticles/polyelectrolyte multilayer films
by AFM and micro-tribometer / Tribology International.- N 44. - P. 906–915. - 2011.
135
P25
SYNTHESIS OF N-(PICRYLAMINO)NITROPYRAZOLES
I.L. Dalinger, I.A. Vatsadze, T.K. Shkineva, A.V. Kormanov, S.A. Shevelev
N.D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences, Laboratory of
Nitrogen-containing Aromatic Compounds, Moscow, Russian Federation
One of the directions of modern design of nitroazole-based high-energy compounds consists in the
introduction of an N-amino group to the endocyclic nitrogen atom of the nitroazole ring. This
results in the preparation of N-amino derivatives of nitrotetrazole [1], nitrotriazoles [1-3],
nitroimidazoles [4], and nitropyrazoles [3, 5-8].
However, the possibility functionalization N-aminonitroazoles additional energy-rich groups with
saving of nitro groups in azole cycle poorly understood and limited only N-nitration [4a], Ntrinitroethylation [3, 4c] and the introduction of a fragment of [1,2,4]triazolo[4,3-b][1,2,4,5]tetrazine [9].
In continuation of our works on chemistry of polynitropyrazoles [10] and for the purpose of
broadening of synthetic potential of N-aminonitroazoles as versatile building-blocks for
constructing new energy-rich compounds we developed method functionalization N-amino group
using picryl fragment on the example of N-aminonitropyrazoles 1.
This method is based on arylation N-aminonitropyrazoles 1 under the action of picrylchlorid (PicCl)
in the presence of base (К2СО3) when heated in MeCN within 2-6 h. The result is synthesized
representatives of a previously unknown type of energy-rich compounds - N(picrylamino)nitroazoles 2, which are isomers well known C-(picrylamino)nitroazoles [11].
Compounds 2 with two nitro groups in the pyrazole ring are organic NH-acids medium strength
(рКа 4.0 - 4.5, in MeCN-Н2О).
[1] T.M. Klapötke, D.G. Piercey, J. Strierstorfer, Dalton Trans., 2012, 41, 9451.
[2] P. Yin, Y. Zhang, D.A. Parrish, J.M. Shreeve, J. Mater. Chem. A, 2013, 1, 585.
[3] Y. Zhang, D.A. Parrish, J.M. Shreeve, J. Mater. Chem. A, 2014, 2, 3200
[4] (a) R. Duddu., P.R. Dave, R. Domavarapy, N. Gelber, D. Parrish, Tetrahedron Letters, 2010, 51, 399; (b)
M.M. Breiner, D.E. Chavez, D.A. Parrish, Synlett, 2013, 24, 519; (c) P. Yin, Y. Zhang, Y. Zhang, D.A.
Parrish, J.M. Shreeve, J. Mater. Chem. A, 2013, 1, 7500.
[5] G. Hervé, C. Roussel, H. Graindorge, Angew. Chem., Int. Ed. Engl., 2010, 49, 3177
[6] C. He, J. Zhang, D.A. Parrish, J.M. Shreeve, J. Mater. Chem. A, 2013, 1, 2863.
[7] V.M. Vinogradov, I.L. Dalinger, S.A. Shevelev, Mendeleev Commun., 1993, 111.
[8] X. Zhao, C. Qi, L. Zhang, Y. Wang, S. Li, F. Zhao, S. Pang, Molecules, 2014, 19, 896.
[7] N.V. Palysaeva, K.P. Kumpan, M.I. Struchkova, I.L. Dalinger, A.V. Kormanov, N.S. Aleksandrova,
V.M. Chernyshev, D.F. Pyreu, K.Yu. Suponitsky, A.B. Sheremetev, Оrg. Lett., 2014, 16, 406.
[10] (a) I.L. Dalinger, I.A. Vatsadze, T.K. Shkineva, G.P. Popova, S.A. Shevelev, Synthesis, 2012, 44, 2058;
(b) I.L. Dalinger, I.A. Vatsadze, T.K. Shkineva, G.P. Popova, S.A. Shevelev, Y.V. Nelyubina, J.
Heterocycl. Chem., 2013, 59, 911.
[11] (a) P.N. Neuman, J. Heterocycl. Chem., 1970, 7, 1159; (b) M.D. Coburn, J. Heterocycl. Chem., 1970, 7,
345 and 1971, 8, 153.
The research was supported by the Division of Chem. and Material Sciences of the RAS (OKh-4).
136
P26
MeLaOX/ZrO2 CATALYSTS FOR CO OXIDATION
N.A. Davshan, A.L. Kustov, O.P. Tkachenko, L.M. Kustov
IOC RAS, Lab.14, Moscow, Russia
Mixed metal oxides with a composition АВО3 known as perovskites exhibit the high thermal
stability and enhanced catalytic activity in CO and hydrocarbon oxidation. The perovskite-type
materials are less expensive as compared to supported noble metals. The materials can be
significantly improved by supporting the perovskites onto porous carriers with a developed surface
area. The goal of our work was to prepare, characterize and test in CO oxidation a series of MeLaO3
perovskites (Me = Co, Fe, Ni) supported onto a mesoporous zirconia as a robust and durable carrier.
The synthesis of mesoporous ZrO2 was carried out according to the previously developed and
modified procedure [1]. A glycine complex of lanthanum and cobalt or iron or nickel was prepared
by the recipe described in [2, 3]. The samples of supported lanthanum-metal perovskites were
prepared by impregnation of the precalcined mesoporous carrier (ZrO2) with a solution of the
prepared La-Co/Fe/Ni glycine complex.
The chemical analysis of the samples for the contents of the metals (Zr, Co, Ni, Fe, and La) was
carried out by atomic emission spectroscopy.
Diffuse-reflectance FTIR spectra were recorded at room temperature in the frequency range of
6000-400 cm-1 with a resolution of 4 cm-1 using а NICOLET “Protege” 460 spectrometer supplied
with a diffuse-reflectance attachment. The following probe molecules were used to test surface sites
of different nature: СО as a probe for Lewis acid sites and low-coordinated metal ions, CD3CN as a
probe for both Lewis and Broensted (if present) acid sites. The probe molecules were adsorbed at
room temperature and equilibrium pressures of 5 Torr for СО, 96 Torr for CD3CN (saturated
pressures).
The phase composition of the samples and the particle size of the supported metal were examined
by X-ray diffraction (XRD) analysis. X-ray absorption (XANES + EXAFS) spectra (Co K edge at
7709 eV and Ni K edge at 8333 eV) were measured at the Hasylab X1 station (DESY,Germany)
using a Si(111) double crystal monochromator. The EXAFS data analysis was performed using the
software VIPER [4]. Reference spectra were taken using standard reference compounds: CoO,
Co3O4, Co-foil, NiO, and Ni -foil. The required scattering amplitudes and phase shifts were
calculated by the ab initio FEFF8.10 code [6]. X-ray photoelectron spectra were recorded by XSAM
800 spectrometer with Mg Kα X-ray (1253.6 eV) source.
Catalyst testing was carried out in a laboratory scale fixed bed quartz reactor (internal diameter 3
mm), operating at an atmospheric pressure. The feed gas mixture consisted of 4.5 vol. % CO, 22.5
vol. % O2 and He balance. The total feed flow rate was held constant at 10 cm3/min, with a volume
hourly space velocity (VHSV) of 6000 h−1.
The following order of the activity in CO oxidation, as the temperature of the 50% conversion (T50),
was found in the temperature range from 50 to 400°C: LaCoO3/ZrO2 (200oC) > LaFeO3/ZrO2
(275oC) > LaNiO3/ZrO2(300oC).
[1] V. A. Sadykov, L. A. Isupova, I. A. Zolotarskii, L. N. Bobrova, A. S. Noskov, V. N. Parmon, E.
A. Brushtein, T. V. Telyatnikova, V. I. Chernyshev, V. V. Lunin, Appl. Catal.A 204 (2000) 59.
[2] E.V. Makshina, Thesis of Cand. Sci. Dissertation, Moscow State Univ., 2008.
[3] L.M. Kustov, Top. Catal. 4 (1997) 131.
[4] K.V. Klementiev, www.cell.es/Beamlines/CLAESS/software/viper.html
[5] A.L. Ankudinov, B. Ravel, J.J. Rehr, S.D. Conradson, Phys. Rev. B, 58 (1998) 7565.
137
P27
SELECTIVE FUNCTIONALIZATION OF ALKYNES WITH NATURALLY
OCCURRING ORGANOSULFUR COMPOUNDS
E.S. Degtyareva, V.P. Ananikov
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Nowadays crude oil remains one of the most important resources in the industry. Crude oil is a
complex mixture mostly of hydrocarbons with small amounts of sulfur- and nitrogen-containing
impurities. To produce more valuable fuels, oil fractions are subject to catalytic processes, like
reforming, isomerization, and cracking. For ecological as well as technological reasons
organosulfur components should be removed before the petroleum refining. However, it would be
much more interesting to utilize these sulfur species as a naturally-occurring source of chemical
reagents, for example for functionalization of hydrocarbons.
The promising and efficient way to create a C-S bond is an addition reaction of thiols and disulfides
to unsaturated hydrocarbons [1,2]. A convenient and selective metal-catalyzed methods for the
addition of thiols and disulfides to alkynes have been recently reported. The present study is
dedicated to the development of such catalytic system in order to involve crude oil as a reagent in
organic synthesis.
As the first step in our study we describe analytic approach for high sensitivity mass spectrometric
measurements with ability to detect trace amount of products. Since most of the components in the
crude oil are nonpolar, special polar tags were introduced for electrospray ionization (ESI)
detection. To achieve this aim the alkynes with easily polarizable groups were synthesized. Good
results were achieved using 1-(pentyn-4)-1H-imidazole, and in the model reaction involving the
mixture of C6H5SH, C6H11SH and C6H13SH all products were clearly detected (Figure 1). Detailed
study of the catalytic system and ESI-MS characterization will be presented and discussed.
Figure 1. An example of ESI spectrum registered for the reaction mixture in the crude oil.
(1) Ananikov, V. P.; Kabeshov, M. A.; Beletskaya, I. P.; Khrustalev, V. N.; Antipin, M. Y. Organometallics
2005, 24, 1275–1283.
(2) Ananikov, V. P.; Orlov, N. V; Zalesskiy, S. S.; Beletskaya, I. P.; Khrustalev, V. N.; Morokuma, K.;
Musaev, D. G. J. Am. Chem. Soc. 2012, 134, 6637–6649.
138
P28
PLATINUM GROUP METALS COMPLEXES OF HYBRID CHALCOGEN
LIGANDS: SYNTHESES, STRUCTURES AND CATALYSTS IN C-C
COUPLING REACTIONS
S. Dey
Chemistry Division, Bhabha Atomic Research Centre, Mumbai- 400 085, India
The chemistry of chalcogenated platinum group metal complexes has been of considerable interest
for several years due to their fascinating structural features, their relevance in catalysis [1] and
lately in materials science [2,3]. These complexes are mostly non-volatile, insoluble or poorly
soluble oligomeric species in organic solvents, thus limiting their utility as precursors for the
synthesis of metal chacogenides for electronic devices or making them inconvenient for any
homogeneous catalysis reaction. To inhibit polymerization of metal chalcogenolates and to develop
phosphine free Pd-catalysts, internally functionalized ligands, containing both soft chalcogen and
hard N donor atoms has been quite successful, such as pyridine chalcogenolates [4] or aliphatic
amine chalcogenolate ligands [5,6].
We have designed and developed several internally functionalized ligands (N E)2, N EAr (E = S,
Se, Te; N E = Me2NCH2CH2E, Me2NCH2CH2CH2E; Ar = Ph, tol, Mes) and bis(4pyridyl)dichalcogenide and synthesized their palladium(II) and platinum(II) complexes. Versatile
coordination behaviour of these ligands are shown in their complexes (Chart 1). The unusual colour
of [MCl(E N)(PR3)] (blue-violet: Pd, red: Pt) has been attributed due to metal mediated ligand (E)
– to – ligand (PR3) charge transfer transitions. The cationic complexes [Pt(PEt3)2(py2E2)]2(CF3SO3)4
with Pt pyridyl bond have been isolated via self-assembly reaction. The complexes
[PdCl2(N EAr)]n exist in monomer and dimer forms, their ratio depends on the size of chelate ring
and chalcogen atom. The catalytic activity of [PdX(N E)]n (X = Cl, OAc), [PdCl2(N EAr)]n and
trans-[PdCl(4-Sepy)(PPh3)2] in Suzuki C C cross coupling reaction will also be discussed.
Chart
E
N
E
M
M
E
X
E
M
M
N
X
X
M
X
+4
E
M
N
E
X
E
M
M
N
E
Ar
N
X
Ar
N
N
N
M
N
N
E
N
N
M
E
E
E
N
E
M
M
N
E
Acknowledgement:
Dilip Paluru, K. V. Vivekananda, A. Wadawale, N. Bhuvanesh, B. M. Bhanage and V. K. Jain are
acknowledged for collaborations.
References
1. Q. Yao, E. P. Kinney, C. Zheng, Org. Lett. 2004, 6, 2997 2999.
2. S. Dey, V. K. Jain, Platinum Met. Rev. 2004, 48, 16 29.
3. B. Radha, G. U. Kulkarni, Adv. Funct. Mater. 2010, 20, 879 884.
4. K. V. Vivekananda, S. Dey, A. Wadawale, N. Bhuvanesh, V. K. Jain, Dalton Trans., 2013, 42,
14158 14167.
5. D. K. Paluru, S. Dey, A. Wadawale , V. K. Jain, J. Organomet. Chem. 2013, 728, 52 56.
6. B. J. Khairnar, S. Dey, V. K. Jain, B. M. Bhanage, Tetrahedron Lett. 2014, 55, 716 719.
139
P29
THE REACTIONS OF 1,3-DIARYL-3-CYCLOHEXANONILPROPANE-1ONE WITH HYDROGEN SELENIDE IN SITU IN CONDITIONS OF ACID
CATALYSIS
D.Yu. Direnko1, Ya.B. Drevko2, B.I. Drevko2
1 - Penza branch of the military Academy of logistics
2 - FGU VPO Saratov State Agrarian University named after N.I. Vavilov
It is known that when arylaliphatic 1,5-dicetones interacts with hydrogen selenide in conditions of
acid catalysis the corresponding 4H-selenopyran structures can be formed 1, which are used as
veterinary and healthcare products. However, dicyclic diaryl-4H-selenopyrans have not been
described until today.
We have studied the chemical reaction of 1-paramethoxy-3-phenyl-3-cyclohexanonilpropane-1-one
1 with hydrogen selenide in situ in conditions of acid catalysis. The reaction has been conducted in
the presence trimethoxyphosphine 1. In the result of the compound 1 was obtained in 2paramethoxy-4-phenyl-5,6,7,8-tetrahydro-4H-selenochromen 2 with quantitative output – 80%
(Melting point = 108-1090С).
Ph
Ph
C H 3OH
O O
Ph - OCH
3
PCl3
ZnSe
Se
p
Ph - OCH p
3
2
1
In the course of reaction settled crystal compounds and mother solution were analyzed by method
of the capillary gas-liquid partition chromatography with mass-selective detector HP 5890/5972:
Tinj=200оС, tset=3 min; Tset=50 оС; Tend=280 оС; Т = 10 оС/min; carrier gas – helium,
= 1 ml/min.
It was found that every molecular ion or fragment which contained selenium presented in the form
of six signal intensities conforming to the content of the selenium isotopes in the nature: Se74
(0,87%), Se76 (9,02%), Se77 (7,58%), Se78 (23,52%), Se80 (49,82%), Se82 (9,19%).
The compound 2 is subjected to isomerisation at high temperature. So, there are signals of four
compounds with retention time 27,03 min, 29,06 min, 29,3 min, 40,08 min on the chromatogram
(m/z = 381, the output of this molecular ion is accompanied by loss of one hydrogen’s isotope).
As well as, one compound was identified and its molecular ion was conformed to
dehydroselenochromen (m/z = 380, retention time is 33,35 min). This ion also was identified
through GH-MS that confirmed the received mass spectrum.
Therefore formation of product (dehydroselenochromen (m/z = 380)) demonstrates the new
direction of disproportionation of dehydroselenochromen structures on alicyclic fragment.
Literature
1. Drevko Ya.B., Fedotova O.V. The synthesis of the first representatives of benzenediamine
dehydroselenochromens // CHC.2006.№10.P.1586-1587.
140
P30
SYNTHESIS OF UNNATURAL PROLINE DERIVATIVES USING THE AZACOPE-MANNICH-REACTION
D.S. Belov, N.K. Ratmanova, A.V. Kurkin, I.A. Andreev
Lomonosov Moscow State University
Oxygenated bicyclic amino acids constitute an important class of secondary metabolites. Many of
these nonproteinogenic amino acids are subunits of structurally diverse natural products. Various
methods to access these biologically important compounds were advised by synthetic community
and subsequently used by pharmaceutical companies. However pharmaceutical industry usually
relies on the most robust and reliable reactions.
Aza-Cope-Mannich rearrangement is a powerful reaction which was successfully used in academia
settings, was however largely overlooked by medicinal chemists.1 We have shown recently that it
can be routinely scaled up to 1 mole.2,3 In this work we demonstrated that a number of proline
analogs can be efficiently prepared with full control of stereochemistry.
Scheme 1.
The aminoalcohols required for the rearrangement were effectively prepared in several steps form
commercially available oxiranes (Scheme 1). The aza-Cope-Mannich reaction provided both cis and
trans fused unnatural proline analogs 2, 3 or 4 in high yields. The ratio of products was dependent
upon the reaction conditions and the nature of substituents R1 and R2. The reaction also proved to
be scalable (>1 g).
This study was supported by the Russian Foundation for Basic Research. (Projects No. 14-0331685, 14-03- 31709, 14-03-01114).
1. Overman, L. E.; Humphreys, P. G.; Welmaker, G. S. Org. React. 2011, 75, 747-820.
2. Belov, D. S.; Lukyanenko, E. R.; Kurkin, A. V.; Yurovskaya, M. A. Tetrahedron 2011, 67,
9214–9218.
3. Belov, D. S.; Lukyanenko, E. R.; Kurkin, A. V.; Yurovskaya, M. A. J. Org. Chem. 2012, 77,
10125–10134.
141
P31
SYNTHESIS OF OXYGENATES OF DIFFERENT CLASSES ON
HETEROGENIOUS KCOMOS-CATALYSTS
V.S. Dorokhov, O.L. Eliseev, A.L. Lapidus, V.M. Kogan
N. D. Zelinsky institute of organic chemistry, Moscow, Russia
Heterogeneous catalytic systems based on alkali-modified molybdenum disulphide are promising
for alcohols synthesis from СО and Н2 [1,2]. The model of dynamic nature of the active sites of
transition metal sulphide catalysts was taken as a conceptual basis for the work [3].
We conducted investigations of structure and functioning mechanism of MoS2-based catalysts
active phase in oxygenates synthesis reaction. We found out that alkali metal (potassium) forms
unite phase with MoS2 and significantly changes it structure. Addition of potassium increases
average number of layers and average linear size of MoS2 crystallites. As it follows from our
catalytic experiments, both Co and K increases selectivity of alcohols formation. Besides addition
of potassium suppresses hydrogenation and hydrodesulphurisation reactions [4].
We suggested that formation of alcohols from СО and Н2 occurs on active sites located on the
"edges" of the MoS2 slabs. It is likely that active sites responsible for alcohols synthesis consist of a
combination of two MoS2 clusters, one of which is promoted with Co, and K is intercalated
between the crystallite layers. Formation of alcohol molecule depends on accessibility of alkali ion
to coordination of alcoxyl intermediate oxygen. The scheme of possible mechanism of synthesisgas conversion on KCoMoS catalyst was published in [5].
The addition of ethanol or ethylene to synthesis gas substantially changes the reaction rate and
composition of the products [5]. Presence of these components in the gas feed can significantly
increase CO conversion. According to our results alcohols can adsorb on KCoMoS-catalysts active
sites and enter a series of side reactions, which leads to formation of ethers, esters, aldehydes,
ketones and organic acids. Therefore, the use of additives to syngas makes it possible to obtain a
wide range of oxygenates of different classes. The further development of this approach can be
efficient for controlling selectivity in processes of simultaneous synthesis of various classes of
organic compounds.
Acknowledgment. This work was financially supported by the Russian Foundation for Basic
Research (Project No. 14-03-31769 mol_a).
References:
1) Surisetty V.R. et al. App. Cat. A 404 (2011) 1-11.
2) Feng M. Recent Patents Catal. 1 (2012) 13-26.
3) Kogan V.M., Nikulshin P.A., Rozhdestvenskaya N.N. Fuel 100 (2012) 2–16.
4) Dorokhov V.S. et al. Kinetics and Catalysis 54 N 2 (2013) 243–252.
5) Kogan V.M. et al. Russ. Chem. Bull. № 2 (2014) in press.
142
P32
THE MECHANISM OF ALCOHOL FORMATION OVER TMS CATALYSTS
V.S. Dorokhov1, E.A. Permyakov1, O.L. Eliseev2, V.M. Kogan1
1 - N.D. Zelinsky Institute of Organic Chemistry, RAS, Laboratory of catalysis by trasition metals
and their compounds, Moscow, Russia
2 - N.D. Zelinsky Institute of Organic Chemistry, RAS, Laboratory of catalytic reaction of carbon
oxides, Moscow, Russia
The aim of this work is to investigate a structure of transitional metal sulfide (TMS) catalyst active
sites in mixed alcohol synthesis (MAS) from synthesis gas and to develop possible mechanism of
this reaction. The model of dynamic nature of the active sites of TMS catalysts was taken as a
conceptual basis for the work [1,2]. As it follows from our catalytic experiments, both Co and K
affect alcohol selectivity towards hydrocarbon (HC) formation. It is likely that the active sites
responsible for alcohol formation are located on the "edges" of the MoS2 slabs. Besides, K poisons
C-S hydrogenolysis sites and HDS activity decreases. Basing on the experimental data, we suggest
the structure of the MAS site as a combination of two MoS2 clusters, one of which is promoted with
Co, and K is intercalated between the crystallite layers and the scheme of possible mechanism of
synthesis-gas conversion on K-Co-Mo-S catalysts (Fig. 1).
H
H 2C
O
Mo
e ffe c t o f K , C o a n d s u p p o rt
H
H
S
S
S
S
C
K
S
S
S
S
S
O
Mo
Mo
K
S
S
H
H
C n H 2n+1 M o
Co
S
S
K
S
S
CH3
S
Mo
Mo
S
S
H
O
S
S
H
Mo
S
H
C
S
S
S
S
O
CH2
S
K
S
S
Mo
Co
S
O
2H S
C n-1 H 2n-2
C
3H
S
S
H
S
nC
O
O
Mo
S
S (n -1 )H O
2
(4 n -4 )H
S
S
Mo
H 2O
S
S
C
S
H
S
Mo
Mo
S
Mo
H
K
K
K
S
S
CH3
S
Co
Mo
Co
Mo
Mo
Mo
K
S
CH4
S
S
H 2O
H 3C
S
Mo
Mo
K
S
Mo
Co
S
O
S
S
Mo
H
Mo
Mo
K
S
S
Co
Mo
Co
CH2
Mo
Mo
S
S
S
2H
Mo
Mo
Mo
H
C n H 2n+1
Mo
O
K
H
Co
S
O
C
S
CH 3 OH
3H
C
C
Mo
Mo
C n+1 H 2n+4
S
S
H
Co
S
Mo
Mo
Co
S
S
K
S
S
S
H
Mo
Co
H
S
C n+1 H 2n+3 OH
Mo
ef
fe
an ct
d of
su K
pp , C
or o
t
C n H 2n+1
Co
S
S
S
Fig. 1: Suggested
mechanism of
alcohols and HC
formation over
KCoMoS active
sites. Black
rectangle defines
the initial step of
reaction.
As an initial step of the mechanism, CO adsorption on the vacancy was taken. After partial
hydrogenation of carbon by dissociatively adsorbed hydrogen, the C=O bond lengthens allowing
the oxygen atom to coordinate on K+ ion intercalated between the MoS2 crystallite layers.
Coordination of the oxygen on the K+ ion stabilizes the alkoxylenated intermediate and prevents the
C-O bond from breaking, which is necessary for the succeeding process of alcohol formation.
Oxygen coordination onto the Mo atom of the neighboring cluster leads to hydrogenolysis of the CO bond. The alkyl fragment can either be hydrogenated to form HC or take part in the carbon-chain
growth – next CO molecule is inserted between C and Mo. Oxygen of a newly inserted CO can
coordinate on K or Mo determining formation of either alcohols or HC. It was found that the ratio
of alcohols to HC yields decreases with an increase of reaction temperature. It means that alcohols
formation becomes kinetically less favorable at higher temperatures than the C-O bond
hydrogenolysis. This observation is in agreement with the suggested mechanism.
[1] V.M. Kogan, P.A. Nikulshin, N.N. Rozhdestvenskaya, Fuel 100 (2012) 2–16.
[2] V.M. Kogan, P.A. Nikulshin, Catal. Today 149 (2010) 224–231.
143
P33
CATALYTIC CYCLOMAGNESIATION OF 1,2-DIENES IN THE
SYNTHESIS OF PHEROMONES AND ACETOGENINE’S PRECURSORS
V.A. Dyakonov, A.A. Makarov, O.A. Trapeznikova, U.M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences; Laboratory Catalytic
Synthesys; Ufa; Russia
An efficient method for the synthesis of valuable N-, О-, and Si-containing 1Z,5Z-diene compounds
was developed. The method comprises Cp2TiCl2-catalyzed cross-cyclomagnesiation of 1,2-dienes
by Grignard reagents (RMgR’) to give 2,5-dialkylidenemagnesacyclopentanes in up to 96% yields.
This approach was successfully used in the synthesis of 5Z,9Z-dienoic acids, precursors of
acetogenins and insect pheromones
Q
()n
.
[ T i] , M g
1
+
E tM g B r
Q
.
R
Q
()n
Mg
3
R
H 3O +(D 3O +)
R
()n
4
2
[ T i] = C p 2 T iC l 2 ; n = 1 , Q = T M S : R = B n ( k ) , H e x ( l) ; n = 2 : Q = O B n , R = H e x ( a ) ; Q = O T H P , R = H e x ( b ) ; Q =
O T H P , R = B n ( c ) ; Q = M o r p h , R = B n ( h ) ; Q = M o r p h , R = H e x ( i) n = 3 : Q = T H P , R = C 1 2 H 2 5 ( d ) ; n = 4 : Q = T H P ,
R = B u ( e ) ; Q = T H P , R = H e x ( f) ; n = 6 : Q = T H P , R = B u ( g ) .
Acylation of diene 4g with acetyl bromide gave hexadeca-7Z,11Z-dien-1-yl acetate 5, the pink
bollworm Pectinophora gossypiella attractant, in a final yield of 89%.
.
T H P O -( C H 2) 6
E tM g B r
[ T i] , M g
+
T H P O -( C H 2) 6
( C H 2) 3 M e
.
94%
Mg
3g
O
( C H 2) 3 M e
T H P O -( C H 2) 6
H 3O +
( C H 2) 3 M e
Me
Br
89%
( C H 2) 3 M e
A c O -( C H 2) 6
4g
5
The same approach was used to obtain the key synthons in the preparation of some acetogenins
exhibiting high antitumor, antimalarial, and immunosuppressive activities. Cross cyclomagnesiation
of 1,2-hexadecane and 2-(4,5-hexadiene-1-yloxy)tetrahydropyran followed by hydrolysis furnished
2-(hexacosa-4Z,8Z-dien-1-yloxy)tetrahydropyran 4h (yield 84%), which is the key intermediate in
the preparation of the acetogenin cis-Solamin 6.
.
( )10
+
THPO
( )2
E t M g B r , [ T i]
.
( )2
( )10
2 0 oC , E t 2 O
Mg
H 3O +
OTHP
87%
3h
O
( )2
( )10
H 23 C 12
OTHP
4h
HO
H
O
( )11
H
OH
O
6
This work was performed under financial support from the Russian Science Fondation (Grant 1413-00263) and by Russian Foundation for Basic Research (Grant 14-03-97024)
144
P34
SYNTHESIS AND ANTIHELMINTIC ACTIVITY OF 5-O-DERIVATIVES OF
IVERMECTIN
I.V. Zavarzin1, M.Kh. Dzhafarov2, N.V. Krukovskaya1
1 - N.D. Zelinsky Institute of Organic Chemistry, RAS, Moscow, Russia
2 - K.I. Skryabin Moscow State Academy of Veterinary Medicine and Biotechnology, Moscow,
Russia
Ivermectin 1 and its derivatives are widely used as antihelmintic medical formulations. In this case,
the parasites eventually develop resistance to these substances.1,2 It is therefore highly relevant to
develop new antihelmintic agents. We were the first who obtained the 5-O-ivermectin derivatives 2
by acylation of an ivermectin 1 anhydrides of carboxylic acids. In addition to the carboxylic acids
the corresponding esters and amides are also obtained.
R
MeO
C H3
O
O
O
H3 C
C H3
HO
H3 C
O
OMe
OH
O
O
O
1: R =M e, Et R 1=H
2: R =M e, Et
C H3
O
O
O
C H3
R1
O
O
C H3
R 1=
OH
Carboxylic acid 2, as well as their esters and amides show high antihelmintic activity.
Literature:
1. Tyrell К., Leo F., Veterinary Parasitology. - 2009. - №11. - Р. 98-102.
2. Varady M., Cobra J., Letkova V., Kovac G., Veterinary Parasitology. - 2009. - №2-3. – Р. 267271.
145
P35
TRENDS IN EVOLUTION OF ANTIPARASITIC CHEMICAL AGENTS
M.Kh Dzhafarov
K.I. Skryabin Moscow State Academy of Veterinary Medicine and biotechnology
Chemotherapy and prevention are of high priority in control of helminthoses and other dangerous
parasitoses of humans, animals and plants [1].
However, the intensive administration of antiparasitic preparations leads to development of
resistance, which is one of the ways of biochemical adaptation of helminths, insects and arthopods
to the first- and second-order environmental changes (the host and ecological niche occupied by the
host, where certain stages of the complex-cycle pest metamorphoses take place), which necessitates
regular renewal of the range of chemical agents, among different measures [2].
Systematization of the data on the antiparasitic substances in the light of new discoveries and
developments is an important step for a successful struggle against parasitic diseases.
In particular, based on the systemic analysis of features of the chemical structure of anthelminthic
substances, the hypothesis on the viability of the targeted search for such compounds among the
derivatives of conditionally progenitor cyclic hydrocarbons – benzene, indene, naphthalene, 1Нcyclopenth [a]-naphthalene, anthracene and phenanthrene – by alternating absolutely unsaturated
and saturated structures, including heterocyclic analogues containing nitrogen, oxygen and sulfur
and different substitutes and functional groups, was voiced:
References
1. Dzhafarov M.Kh. Russian J. Agrobiology. Animal biology series. 2013, №4, p.26-44.
2. Dzhafarov M.Kh., Vasilevich F.I. Advances in Pharmacology and Pharmacy. 2014, 2: 30-45.
146
P36
RHODIUM-CATALYZED REDUCTIVE CARBONYLATION OF
IODOBENZENE
O.L. Eliseev, T.N. Bondarenko, T.N. Myshenkova, A.L. Lapidus
N.D.Zelinsky Institute of organic chamistry, Moscow, Russia
Aromatic aldehydes is useful class of products because of diverse reactivity of formyl group.
Usually they are synthesized by Gattermann–Koch, Reimer–Tiemann, Vielsmeier–Haag, and Duff
reactions. However, these methods suffers from drawbacks like low yield, poor selectivity and
generating waste and side products.1,2 Alternatively, catalytic formylation (reductive carbonylation)
of aryl halides with synthesis gas in the presence of palladium phosphine complexes was firhst
reported in 1974 by Schoenberg and Heck3 and lately by Beller4–6 and Nagarkar7 groups.
Somewhat surprisingly, up to now rhodium was unexplored as a catalyst for reductive
carbonylation of aryl halides. This encouraged us to test rhodium salts and complexes in reductive
carbonylation of iodobenzene as a model substrate.
I
CHO
R h -c a t.
+ CO + H2
+ b aseH I
base
Rhodium phosphine complexes such as HRh(CO)(PPh3)3 and RhCl(CO)(PPh3)2 were found to be
excellent catalysts They surpass PdCl2(PPh3)2 in respect to activity and selectivity to benzaldehyde.
Aromatic solvents such as toluene and o-xylene seems to be the most suitable medium Other
solvents such as heptane, 1,4-dioxane, MEK, DMF and acetonitrile gave poor yield of
benzaldehyde. In methanol solution, methyl benzoate was the main product.
Reaction is highly sensitive to the nature of the base. Replacing NEt3 with NBu3 resulted in almost
threefold reduction in benzaldehyde yield. Somewhat higher but still low yield was achieved with
Hünig's base. Inorganic bases such as potassium and cesium carbonates gave poor iodobenzene
conversion and benzaldehyde yield.
Synthesis gas pressure renders effect on reaction. Iodobenzene conversion reaches 100% at a total
pressure of about 1–1.5 MPa and slightly decreases at higher pressure. Both selectivity and yield of
benzaldehyde increase with pressure increasing while selectivity to benzene decreased. Biphenyl is
a main product at atmospheric pressure but it fully disappears at a pressure 1 MPa and higher.
In conclusion, rhodium (I) triphenylphosphine complexes are good catalysts for reductive
carbonylation of iodobenzene. The best catalyst formulation found: 0.5% RhCl(CO)(PPh3)2, 150%
NEt3, toluene. At 110°C and 1.5 MPa (CO/H2 = 1/1) iodobenzene is totally converted within 2
hours giving benzaldehyde with the yield of 88%.
References
1. F. Aldabbagh, Compr. Org. Funct. Group Transform. II, 2005, 3, 99.
2. L. P. Crawford, S. K. Richardson, Gen. Synth. Methods, 1994, 16, 37.
3. A. Schoenberg, R. F. Heck, J. Am. Chem. Soc., 1974, 96, 7761.
4. S. Klaus, H. Neumann, A. Zapf, D. Sturbing, S. Hubner, J. Almena, T. Riermeier, P. Groß, M.
Sarich, W.-R. Krahnert, K. Rossen, M. Beller, Angew. Chem. Int. Ed., 2006, 45, 154.
5. A. Brennfuhrer, H. Neumann, St. Klaus, T. Riermeier, J. Almenab, M. Beller, Tetrahedron, 2007,
63, 6252.
6. H. Neumann, R. Kadyrov, Xiao-Feng Wu, M. Beller, Chem. Asian J., 2012, 7, 2213.
7. A. S. Singh, B. M. Bhanage, J. M. Nagarkar, Tetrahedron Letters, 2011, 52, 2383.
147
P37
MODELING OF THE ELECTROCHEMICAL IMPEDANCE IN ANODIC
DISSOLUTION OF IRON USING A GENETIC ALGORITHM APPROACH
A.R. Enikeev1, I.M. Gubaidullin2, M.A. Maleeva3
1 - Institute of petrochemistry and catalysis, Laboratory of mathematical chemistry, Ufa, Russia
2 - Institute of petrochemistry and catalysis Laboratory of mathematical chemistry
3 - A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow, Russia
In order to predict the general corrosion damage to metals and alloys, development of deterministic
models and the acquisition of values for various model parameters are of paramount importance.
Now it is generally accepted that elucidating an intricate reaction mechanism by means of steadystate techniques alone is a very difficult task [1]. In fact, the steady-state approach provides too little
information in comparison with the complexity of the process under investigation. In the present
work, we used model with three adsorbed species it was possible to explain the iron dissolution in
sulphate and chloride media.
It was recently found that impedance diagrams reveal at least three time constants concerning the
faradaic process in the iron-sulphate systems was proposed by Keddam [2].
Reaction mechanis.
The reaction kinetic parameters was calculated by genetic algorithm. The experimental impedance
diagrams showed one high-frequency capacitive arc and three time constant at lower frequencies
appearing as inductive or capacitive loops. They are attributed in the models, respectively, to the
double layer capacitance in parallel with the transfer resistance and to the relaxation of three
reaction intermediates.
1. E J Kelly, J Electrochem Sot 112, 124.
2. M Keddam, R Mattos and H Takenoutl, J Electro-them Sot 128, 257, 266 (1981).
148
P38
KINETICS AND MECHANISM OF THE CATALYTIC OXIDATION OF 4TERT-BUTYLPHENOL BY AQUEOUS SOLUTIONS OF H2O2 IN THE
PRESENCE OF TITANOSILICATES
L.V. Enikeeva, I.M. Gubaydullin, N.F. Murzasheva
Institute of petrochemistry and catalysis RAS, Laboratory of mathematical chemistry, Ufa, Russia
Selective oxidation of phenol is of great interest in terms of education practically valuable product hydroquinone and catechol . This work is part of studies on the oxidation of phenols in aqueous
solutions of hydrogen peroxide in the presence of metallosilicates .
For initial evaluation of the activity of titanosilicate catalysts in oxidation reactions of organic
compounds , we used a decomposition reaction of H2O2 in the absence of substrate. We studied the
catalytic activity in the decomposition reaction metallosilicates H2O2: apparent activation energy of
the reaction in the presence of different samples metallosilicates were calculated; expression for the
reaction rate, which shows good agreement with the experimental data, was proposed; model
validation on the value is performed.
A series of catalytic activity of the samples in the reaction of hydrogen peroxide decomposition was
created.
At the moment we study the oxidation reaction of tretbutilfenola by aqueous solutions of H2O2. The
scheme of the reaction, the reaction kinetic parameters was calculated.
149
P39
NEW CHEMICAL TRANSFORMATIONS OF Ni(acac)2 WITH POSSIBLE
INVOLVEMENT OF SUPERATOMIC Ni2O2 CORE AS REVEALED BY ESIMS AND MS/MS
D.B. Eremin, V.P. Ananikov
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
More than twenty signals of nickel-containing ions were detected upon studying of electrospray
ionization mass spectrum of the Ni(acac)2 sample prepared in a plastic tube. However, changing
sample preparation procedure to a glass vial gave a clear spectrum with four signals corresponding
to: m/z 257.0141, [Ni(acac)2 + Na]+; m/z 413.0040, [Ni2(acac)3] +; m/z 535.03838 [Ni2(acac)4 +
Na]+; and m/z 669.0285, [Ni3(acac)5] + (Figure 1A). A prominent difference in the spectra was
caused by various plastic-derived contaminants, that were coordinated to the metal center.
Figure 1. (A) ESI-MS spectra of solution of Ni(acac)2 in acetonitrile prepared under standard
conditions (with contaminant signals marked by blue symbols) and prepared without a contact with
plastic (m/z = 250 – 1000 range; acac = C5H7O2); (B) Experimental survival yield curves of most
abundant ions.
CID (Collision-induced dissociation) MS/MS experiments were carried out to estimate relative
stability and to study reactivity during fragmentation process. Fragmentation of the bimetallic ion
[Ni2(acac)3] + was of most interest. Eight fragment ions of different composition were detected.
Seven of them were formed as a result of C–C, C–H and C–O bond cleavage; nevertheless, they
retained the Ni2O2 core, a supposed superatomic structure, which caused exceptional behavior
observed in the fragmentation. After the fragmentation at the applied collision energy of 40 eV,
ketene, pentyn-3-on-2, buten-3-on-2, acetaldehyde, carbon monoxide, and hydroxide-anion were
formed. Other bi-, tri- and monometallic species detected did not undergo such transformations
under MS/MS conditions. Survival yields were calculated (Figure 1B), and a series of relative
stability was proposed: Ni2 >> Ni1 ≈ Ni3. The signal of [Ni2(acac)3] + remained as most intensive
after heating of the solution.
Mass spectra with the similar ionic composition were obtained for vanadyl and copper(II)
acetylacetonates as well as after the addition of two-fold excess of acetylacetone to the solution of
the acetates M(OAc)2 (M = Ni, Cu, Pd). Chemical reactivity of detected ions and the role of
bimetallic species are currently under investigation.
150
P40
FORMATION OF A COMPLEX WITH FLUOROGENE LABEL IS A
RELIABLE WAY OF CREATION OF AN EXPRESS-METHOD OF
ACETYLCHOLINESTERASE ACTIVITY ASSAY
O.V. Fateenkova, E.T. Gainulina, D.K. Gulikova, S.B. Ryzhikov, V.N. Fateenkov
I.M. Sechenov First Moscow State Medical University, Faculty of
Pharmacy, Russia, Moscow
Assay of erythrocyte acetylcholinesterase (AChE) activity of human is widely used for the
successful decision of many problems facing to a modern science: development of effective antidots
for treatment of defeats by toxic organophosphorus inhibitors, medicines for treatment of illness
Alzheimer and Parkinson etc.
In a lot of cases there is a necessity of express-analyses of defeat by toxic organophosphorus
inhibitors. As an example it is possible to refer to events in the Tokyo underground in 1985 year
and also in territory of several syrian cities in 2013 year, when in the terrorist purposes sarin has
been applied and there was a necessity of urgent diagnostics of a degree of defeat of significant
number of victims of this act of terrorism.
Known methods of AChE activity assay do not correspond to modern requirements to correlation
of parameters “sensibility - time of formation of an analytical signal».
In the given work the express-method of acetylcholinesterase activity assay is offered on the basis
of formation of an intensively fluorescing complex by the given enzyme with fluorogene label
thioflavine T (TF). TF is reversible inhibitor of AChE and selectively binds to the peripheral site of
this enzyme.
Figure. Dependence of fluorescence intensity of TF (15 М) from AChE activity.
With increase of AChE activity at constant concentration of ТF (15 М) in the investigated interval
of reagents concentrations the dependence of fluorescence intensity of system TF - AChE has
linear character (fig.). At addition AChE to solution TF formation of an analytical signal (increase
of fluorescence intensity) on a wave of 490 nm is observed within of several seconds, and the
achieved of fluorescence intensity remains stable more than 15 min. The absence of influence of
human butirylcholinesterase and bull whey albumin on fluorescence intensity of thioflavine T on
length of a wave of 490 nm is confirms selective character of interaction of human erythrocyte
acetylcholinesterase with TF.
1. De Ferrari G.V., Mallender W.D., Inestrosa N.C., Rosenberry T.L. J. Biol. Chem. 2001. 276, 23282.
2. Antokhin A.M., Gainullina E.T., Taranchenko V.F., Ryzhikov S.B., Yavaeva D.K. Russ. Chem. Rev. 2010. 79. № 8,
713.
151
P41
QUANTUM CHEMICAL MODELING OF CONFORMATIONS OF TERTBUTYL HYDROPEROXIDE
G.T. Garaeva, V.I. Anisimova, I.A. Suvorova, N.N. Batyrshin
Kazan National Research Technological University, 420015, Kazan, K.Marks 68
Data on internal rotation of tert-butyl hydroperoxide (TBHP) advance the field of conformational
analysis and can be used for investigation of reactivity of industrially important hydroperoxides
which are primary products of hydrocarbon oxidation processes.
For TBHP, internal rotation only about C-O and O-O bonds is possible. Earlier it was demosntrated
that TBHP has two conformations – gauche and trans [1]. Figure 1 (curves 1,2) shows that all
possible equilibrium structures of TBHP have identical energy, while analysis of bond lengths and
angles (Table 1) also supports identity of these structures, and, therefore, monomeric form of TBHP
exsists only in one conformation (Fig. 2) [2].
Table 1 – Parameters of TBHP according to B3LYP/6-311++G(df,p) calculations.
Bond length, Å
С-О
О-О
О-Н
Angle, °
СОО ООН
1.450 1.456 0.966 109.5 100.2
Torsion angle,°
OH,
С2С1О1О2
С3С1О1О2
С4С1О1О2
С1ООН
sm-1
-60.1
-178.0
63.8
-122.6
3785
Fig. 1 – PES of internal rotation of BHP:
1- around О-О bond , 2 – around С-О bond
Fig. 2 – Molecule of TBHP
1 Suvorov, I. A Association and the thermal decomposition of tertiary hydroperoxides: Thesis
Candidate. chem. sci./I.A. Suvorov. - Kazan, 2003 - 124 p.
2 Anisimov, V.I. Quantum-chemical study of the hydrogen bonds between molecules tertiary butyl
hydroperoxide // V.I. Anisimova, I.A. Suvorov, N.N. Batirshin, V.I. Sokolov, K.E. Kharlampidi
// Vestnik Bashkir University. - 2008 - v. 13. -№3 (1). - p. 793-797.
The work was supported by Russian Ministry of Education and Science within the framework of
basic part (PNIL 02.14).
152
P42
SUPRAMOLECULAR INTERACTION OF CAFFEINE MOLECULES WITH
EACH OTHER, WATER MOLECULES AND OXYGEN ATOMS OF
TETRAOXIDOANIONS IN THE NEW COMPOUND COBALT
HEXAHYDRATE DIPERRHENATE CAFFEINE
K.E. German1, M.S. Grigoriev1, G.V. Kolesnikov2, Yu.A. Ustynyuk2, O.I. Slyusar3, Ya.A.
Obruchnikova3, O.S. Kryzhovets3, M.N. Glazkova3
1 - A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow, Russia;
Medical Institute REAVIZ, Moscow, Russia
2 - Lomonosov Moscow State University, Moscow, Russia
3 - Medical Institute REAVIZ, Moscow, Russia
Recently the antitumor and radiosensitizing drugs being caffeine derivatives that penetrate easily
through blood brain barrier have been developed. They are effective with radiation and
chemotherapy treatment for cases of brain tumors. Results of these studies has shown the caffeine
derivatives as perspective source for receiving therapeutic agents to be used in a combined therapy
for primary and metastatic brain tumors. Anyhow the mechanism of caffeine interaction was not
clear. To provide the proper understanding of caffeine action the precise structural data are
necessary. To increase the accuracy of the structural date and to simulate the interaction of caffeine
with tetraoxidoanion and hydration water molecules the synthesis of caffeine cobalt hexahydrate
perrhenate was carried out from saturated water solutions and the single crystal thus obtained were
subjected to X-ray structural study at Bruker KAPPA APEX II diffractometer.
Supramolecular interactions of caffeine molecules with each other, water molecules and oxygen
atoms of tetraoxidoanions as in a new compound of Co(H2O)6[ReO4]2 . caffeine are analyzed in
these study through comparison of the new precise structural data with quantum chemical analyses.
The reasons for alterable orientation of caffeine molecules to each other and for the H-bonds
network formation has been evaluated.
1. Vartanyan L.P., Kolesova M.B., Gornaeva G.F., Pustovalov Yu.I. Caffeine derivatives —
perspective method of the search for anticancer and radiomodifying drugs in combined therapy
for malignant brain tumors // Psychopharmacol. Biol. Narcol. — 2005. — Vol. 5, N 4. — P.
1093–1095. Central Research Institute of Roentgenology and Radiology, Saint Petersburg
153
P43
EFFICIENT CONVERSION OF ALKENYNONES TO 2METHYLENEDIHYDROPYRROLONES
P.R. Golubev, A.S. Pankova
St. Petersburg State University, Institute of chemistry, St. Petersburg, Russia
Earlier we have developed a method for the synthesis of cross-conjugated ketones 2 and
investigated their interaction with common binucleophiles – hydrazines and amidines [1,2]. Our
next goal was to study the reaction of enynones 2 with amines.
It was shown earlier [1,2] that the ethoxymethylene group is the most active center of ketones 2 in
reactions with nucleophiles. In line with this, enamines 3 were obtained on the first stage in
reactions with amines. Various solvents were used successfully in this reaction, but diphenyl ether
was considered to be the most convenient, since in this case both synthetic steps could be performed
in a one-pot fashion without isolation of intermediate enamines 3.
We proposed that thermolysis of enamines 3 could lead to their cyclization via Michael-type
intramolecular addition of amine nitrogen atom to a triple bond. We have found that this reaction
proceeds smoothly at 200 °C as a 5-exo-dig cyclization leading to pyrrolinones 4 as single products
in good to excellent yields. Various amines with alkyl, aryl or heteroaryl substituents were used.
Thus, monoalkylamines are predictably the most active coupling partners, but in this case steric
factors play a crucial role. Nevertheless, even tert-butylamine was employed successfully in this
reaction along with n-alkyl- and (hetero)benzylamines. In case of anilines the reaction outcome was
fully consistent with nucleophilicity of the amine used. Generally, anilines with electron-donating
substituents reacted more readily and provided higher yields than electron-deficient ones, and a
slight decrease of yield was observed when para-substituted aniline was replaced with an
ortho-substituted analogue. Finally, pyrrolidinones 4 with various heteroaromatic substituents at
nitrogen atom can also be obtained.
In conclusion, we offer a straightforward and high-yielding method for the synthesis of previously
unknown 2-methylenedihydropyrrolones.
[1] A.S. Pankova, P.R. Golubev, I.V. Ananyev, M.A. Kuznetsov, Eur. J. Org. Chem. 2012, 30,
5965-5971.
[2] P.R. Golubev, A.S. Pankova, M.A. Kuznetsov, Eur. J. Org. Chem. 2014, 17, 3614-3621.
Authors thank the Russian Scientific Fund for a research grant No. 14-13-00126.
154
P44
THEORETICAL INVESTIGATION OF PALLADIUM-CATALYZED
DIMERIZATION OF ALKYNES: HYDROPALLADATION VS.
CARBOPALLADATION PATHWAYS
E.G. Gordeev, V.P. Ananikov
N.D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences
Catalytic dimerization of terminal alkynes is a waste-free process that allows preparation of enynes
within atom-economic transformation. The key question for practical utilization of the dimerization
approach is to understand the factors responsible for rendering regioselective transformation and
lead in a to a single poduct.
The studied catalytic dimerization of terminal alkynes may involve two mechanisms:
hydropalladation and carbopalladation, which results in two types of products - head-to-head and
head-to-tail dimers. Experimentally it has been found that the presence in the reaction mixture of
carboxylate anion direct the reaction to head-to-tail product only [1]. To reveal the mechanistic
picture we have carried out the quantum-chemical modeling (B3LYP/6-311G (d) & SDD) of the
catalytic dimerization of phenylacetylene including participation of the carboxylate anion.
Theoretical calculations have shown that in the absence of carboxylate anion the reaction proceeds
as hydropalladation and forms head-to-head product, since potential barrier of the hydropalladation
rate-determining step is much smaller than the barrier of the carbopalladation rate-determining step.
The predominant formation of head-to-head product was also determined by kinetic factor: the
energy of the corresponding transition state was smaller as compared to the transition state of
carpbopalladation pathway.
When carboxylate anion (acetate ion was used for modeling) was added to the reaction mixture, the
H lignad at the metal center was blocked that and only carbopalladation pathway become possible.
Indeed, coordination of the carboxylate ion to the palladium atom, leading to the formation of the
ion pair, destabilized head-to-head intermediate complex. As a result, the second phenylacetylene
molecule was not able to enter into the metal coordination sphere. In the case of head-to-tail
intermediate complex such destabilization did not take place.
Theoretical study of complete potential energy surface and comparison with experimental data will
presented and discussed.
References.
[1] Zatolochnaya O.V., Gordeev E.G., Jahier C., Ananikov V.P., Gevorgyan V., Carboxylate
Switch between Hydro- and Carbopalladation Pathways in Regiodivergent Dimerization of
Alkynes, Chem. Eur. J., 2014, DOI: 10.1002/chem.201402809.
Acknowledgement. Cooperation with V. Gevorgyan (UIC, Chicago) and his group is greatly
acknowledged in this project. The support of the Russian Foundation for Basic Research (RFBR 1403-31752) is gratefully acknowledged.
155
P45
CROSS-METATHESIS OF POLYNORBORNENE AND POLY(1OCTENYLENE) AS A NEW ROUTE TO NORBORNENE AND
CYCLOOCTENE MULTIBLOCK COPOLYMERS
M.L. Gringolts, Yu.I. Denisova, G.A. Shandryuk, L.B. Krentsel, A.D. Litmanovich, Ya.V.
Kudryavtsev, E.Sh. Finkelshtein
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Russia
Norbornene (NB) and cyclooctene (COE) are well-known objects in ring-opening metathesis
polymerization (ROMP). Their homopolymers synthesized by ROMP are important commercial
products [1]. Polynorbornene (PNB), which is sold under the trademark Norsorex, has various
special applications. Poly(1-octenylene) (PCOE), known as Vestenamer or polyoctenamer,
possesses unusual properties for an elastomer. At the same time, the ROMP synthesis of NB-COE
copolymers is rather difficult because of considerably different polymerization activities of the
comonomers. This problem can be solved by catalyst modification [2] or using NB with
substituents decreasing its activity [3].
We propose a new approach to the synthesis of NB-COE multiblock copolymers via interchain
cross-metathesis of PNB and PCOE. That approach enabled us to obtain new copolymers using the
1st generation Grubbs’ catalyst Cl2(PCy3)2Ru=CHPh, which is not suitable for copolymerization of
NB and COE.
m
COE
-
COE
PCOE
[R u = C H P h ]
+
C H C l3
a
n
N B -N B
NB
-
6
N B -C O E
c
b
C O E -C O E
NB
PNB
Cross-metathesis between PNB and PCOE has been successfully realized. New NB-COE
multiblock copolymers were identified and characterized by NMR spectroscopy, GPC, and DSC
methods. It was found that in the course of the reaction the average lengths of PNB and PCOE
blocks were decreased, as well as the copolymer molecular weight and crystallinity. For copolymer
of 1:1 composition, Tg, is about -30 oC, which is higher than for PCOE (- 80 oC) and lower than for
PNB (39 oC). The exchange degree (conversion) reached approximately 40-50% in 24 h.
Copolymer characteristics can be controlled by varying concentration of the catalyst.
The work was supported by RFBR (project 14-03-00665)
1. KJ Ivin, JC Mol (1997) Olefin Metathesis and Metathesis Polymerization. Academic Press,
London
2. Marc Bornand und Peter Chen Angew. Chem. 2005, 117, 8123 –8125
3. C.S. Daeffler and R.H. Grubbs Macromolecules 2013, 46, 3288−3292
156
P46
SELECTIVE C=O HYDROGENATION OF ENONES, ENALS, AND
ENOATES
D.G. Gusev, D. Spasyuk
Wilfrid Laurier University, Department of Chemistry, Waterloo, Canada
In the past three years,1-4 we developed catalysts 1 - 3 for the reduction of esters under hydrogen
gas. Complexes 2 and 3 are today’s most efficeint catalysts for this process and have recently
become commercially available (Aldrich catalogue numbers 746339 and 746347).
Here, we disclose the synthetic, structural, and catalytic details of our newest robust, practical, and
efficient H2 hydrogenation catalyst, distinguished by excellent carbonyl selectivity. The air-stable
osmium complex from our laboratory, OsHCl(CO)(NNNP-tBu) (4), is today's most successful
general catalyst for production of unsaturated alcohols from enals, enones, and alkyl enoates under
H2 at 25 - 100 °C, while using 0.01 - 0.05 mol% [Os] preferably without solvent.
References
1. Goussev, D. G.; Spasyuk, D. PCT Patent Application WO 2013/023307 A1.
2. Spasyuk, D.; Smith, S.; Gusev, D. G. Angew. Chem. Int. Ed. 2013, 52, 2538 - 2542.
3. Spasyuk, D.; Gusev, D. G. Organometallics 2012, 31, 5239-5242.
4. Spasyuk, D.; Smith, S.; Gusev, D. G. Angew. Chem. Int. Ed. 2012, 51, 2772-2775.
157
P47
OVERCOMING SELF-DESTRUCTIVE REACTIVITY IN
ORGANOLANTHANIDE COMPLEXES
P.G. Hayes, K.R.D. Johnson, B.L. Kamenz
University of Lethbridge, Department of Chemistry, Lethbridge, Canada
In an effort to prepare organometallic lanthanide complexes that feature new and unusual
properties, we have designed and synthesized several families of pincer ligands comprised of
phosphinimine donors attached to rigid aromatic cores. Rare earth complexes of the ligands have
been prepared and notably, diverse reaction behavior, such as cyclometalative C–H bond activation,
dearomatization and functionalization of ligand pyrimidine rings by 1,5-alkyl migration, and ringopening insertion has been observed. Notably, the evolution of the design of these pincer ligands
has recently yielded a series of thermally stable organolanthanide species that are resistant to
cyclometalation. The synthesis, as well as the reaction chemistry of the corresponding
organometallic complexes, will be presented.
.
158
P48
METALLOPORPHYRIN-INCORPORATED DIPHOSPHINE LIGANDS FOR
METAL ION-BINDING
G.-A. Yu, K.-M. Wong, J.-S. Huang, N. Zhu, C.-M. Che
The University of Hong Kong, Department of Chemistry, Hong Kong
Diphosphine ligands have been widely used in organometallic chemistry and catalysis.1 By
incorporation of functional units such as metallomacrocycles, the resulting functionalized
diphosphines could exhibit unusual properties or binding behavior. In this study, we prepared
several examples of ruthenium porphyrin phosphine complexes [RuII(Por)(dppm)2] (1; Por = TTP,
4-MeO-TPP, F20-TPP; dppm = bis(diphenylphosphino)methane) by a similar method to that
previously reported for their congeners.2 Reaction of complexes 1 with a number of metal
complexes MLn afforded [(LmM)( -dppm)RuII(Por)( -dppm)(MLm)] (2; M = Ag, Au), which have
been characterized by spectroscopic methods including 1H NMR, 31P NMR, and UV/Vis
spectroscopy, and also by X-ray crystal structure determination. The formation of complexes 2 from
complexes 1 demonstrates the role of complexes 1 as a unique type of diphosphine ligands
functionalized with metalloporphyrins (which constitute a large family of metal complexes that
resemble heme cores in biological systems and exhibit a wide variety of applications3). Studies are
underway to explore the properties of this new type of metalloporphyrin-incorporated diphosphine
complexes of transition metals.
References
1 (a) Genet, J.-P.; Ayad, T.; Ratovelomanana-Vidal, V. Chem. Rev. 2014, 114, 2824. (b) Broda,
H.; Hinrichsen, S.; Tuczek, F. Coord. Chem. Rev. 2013, 257, 587. (c) Birkholz, M.-N.; Freixa,
Z.; van Leeuwen, P. W. N. M. Chem. Soc. Rev. 2009, 38, 1099. (d) Freixa, Z.; van Leeuwen, P.
W. N. M. Coord. Chem. Rev. 2008, 252, 1755. (e) Tuczek, F. Adv. Inorg. Chem. 2004, 56, 27. (f)
Bessel, C. A.; Aggarwal, P.; Marschilok, A. C.; Takeuchi, K. J. Chem. Rev. 2001, 101, 1031.
2 Ball, R. G.; Domazetis, G.; Dolphin, D.; James, B. R.; Trotter, J. Inorg. Chem. 1981, 20, 1556.
3 (a) Handbook of Porphyrin Science, Kadish, K. M.; Smith, K. M.; Guilard, R., Eds.; World
Scientific, 2010. (b) The Porphyrin Handbook, Kadish, K. M.; Smith, K. M.; Guilard, R., Eds.;
Academic Press, 2000.
159
P49
SYNTHESIS OF NOVEL ACCEPTOR MOLECULES OF MONO- AND
MULTIADDUCT FULLERENE DERIVATIVES FOR IMPROVING
PHOTOVOLTAIC PERFORMANCE
H.B. Liu, C. Liu
Institute of Chemistry, Chinese Academy of Sciences,CAS Key Laboratory of Organic Solids,
Beijing, P.R. China
Fullerene derivatives are extensively used in organic photovoltaics (OPVs) because of their high
electron affinity and high mobility1 and remarkable properties on photoinduced electron transfer, in
which [6,6]-phenyl C61-butyric acid methyl ester (PC61BM) is the most widely employed material.2
We have successfully synthesized and separated a series of tert-butyl 4-C61-benzoate (t-BCB)
organofullerenes, including monoadduct, diadduct, and triadduct compounds, and investigated their
photophysics, electrochemistry, thermal properties, and high-performance liquid chromatography
analysis.3 The photovoltaic devices were fabricated based on monoadduct, diadduct, and triadduct
products, and the devices based on them exhibited power conversion efficiencies of 2.43%, 0.48%,
and 1.68%, respectively. Methyl 4-C61-benzoate series fullerene materials with low cost and high
yield, including monoadduct and bisadduct compounds were also synthesized and the photovoltaic
devices based on them showed power conversion efficiency of 3.48% and 0.16% respectively.4 This
was the first time to study the dependent relationship on the device performance and the different
isomer numbers. This work supplied new route to design fullerene materials as PCBM’s alternative.
References
1. Yu, G.; Gao, J.; Hummelen, J. C.; Wudl, F.; Heeger, A. J. Science, 1995, 270, 1789.
2. Liu, C.; Xiao, S.; Shu, X.; Li, Y.; Xu, L.; Liu, T.; Yu, Y.; Zhang, L.; Liu, H.; Li, Y. ACS Appl.
Mater. Interfaces, 2012, 4(2),1065.
3. Liu, C.; Xu, L.; Chi, D.; Li, Y.; Liu, H.; Wang, J. ACS Applied Materials & Interfaces, 2013, 5,
1061.
4. Liu, C.; Li, Y. J.; Chi, D.; Chen, S. H.; Liu, T. F.; Wang, J. Z.; Liu, H. B.; Li, Y. L. Fullerenes,
Nanotubes, and Carbon Nanostructures, 2014, 22, 277.
160
P50
THE FIRST EXAMPLE OF THE SYNTHESIS AND STUDY OF 2-[(Z)-1(FERROCENYLMETHOXY)PROP-1-ENYL]-5-ETHENYLIDENE-4,5DIHYDRO-1,3-THIAZOLES BY METHOD OF MALDI MASS
SPECTROMETRY
O.V. Inozemtseva, O.A. Tarasova, N.A. Nedolya, L.V. Klyba, E.R. Sanzheeva, B.A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
1 Favorsky St., Irkutsk 664033, Russian Federation
Earlier
unknown
2-[(Z)-1-(ferrocenylmethoxy)prop-1-enyl]-5-ethenylidene-4,4-dimethyl-4,5dihydro-1,3-thiazole (1), the first representative of ferrocenyl-substituted functionalized 2thiazolines, was obtained in two preparative steps from (ferrocenylmethoxy)allene, isopropyl
isothiocyanate, and propargyl bromide (through synthesis and structural reorganization of
conjugated 2-aza-1,3,5-triene 2 under action of t-BuONa) in 33% yield (not optimized).
Intens. [a.u.]
Intens. [a.u.]
It was shown that the matrix-assisted laser desorption/ionization (MALDI) mass spectrometry can
be appropriate for the study of the low molecular weight thiazoles, in particular, such as compound
1 (with 2,5-dihydroxybenzoic acid as a matrix). In the gas phase under the experiment conditions,
the generation of [2M] and [2M – H2O] ions (M is molecule of thiazole 1) was detected. The
analysis of the fragmentation of these ions in field-free region showed that their decay was mainly
due to both the degradation of thiazole ring and the formation of the ion [FcCH2]+ at m/z 199.
5000
x104
786.469
786.182
B
3
2M
2
4000
1
199.130
313.201 473.353 643.392
0
200
2000
2M - H2O
Intens. [a.u.]
3000
400
600
800
m/z
x104 199.044
1.25
768.338
A
1.00
0.75
0.50
768.312
0.25
313.149
1000
473.156
784.186
0.00
200
400
600
800
m/z
0
767.5
770.0
772.5
775.0
777.5
780.0
782.5
785.0
787.5
790.0
m/z
Mass spectrum MALDI (under the positive mode) of thiazole 1, registered in the mode reflectron.
On the inserts: А – the МS2 spectrum of ion at m/z 768, B – the МS2 spectrum of ion at m/z 786.
The authors are grateful for the financial support from the Russian Foundation for Basic Research
(Grant No. 13-03-00691a).
161
P51
SYNTHESIS AND MASS SPECTRA OF ELECTRON AND CHEMICAL
IONIZATION OF 2-[(Z)-1-METHOXYPROP-1-ENYL]-5-ETHENYLIDENE4,5-DIHYDRO-1,3-THIAZOLE
O.V. Inozemtseva, L.V. Klyba, E.R. Sanzheeva, N.A. Nedolya, O.A. Tarasova, B.A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
1 Favorsky St., Irkutsk 664033, Russian Federation
The behavior of 2-[(Z)-1-methoxyprop-1-enyl]-5-ethenylidene-4,5-dihydro-1,3-thiazoles 1–4,
synthesized for the first time from methoxyallene, isothiocyanates, and propargyl bromide,1 under
electron ionization (EI, 70 eV) and positive ion chemical ionization (PICI, methane) has been
studied.
Principal fragmentation routes of the 4,5-dihydro-1,3-thiazoles 1–4 after EI include a thiazole ring
cleavage (pathway 1) and the loss of alkyl substituent, mainly at position 4 (pathway 2).
For PICI of the compounds 1–4 are typical processes of protonation and electrophilic addition
followed by the loss of the 2-methoxybut-2-enenitrile molecule.
The authors are grateful for the financial support from the Russian Foundation for Basic Research
(Grant No. 13-03-00691a).
1. Nedolya, N. A.; Tarasova, O. A.; Albanov, A. I.; Trofimov, B. A. Tetrahedron Lett. 2014, 55,
2495–2498.
162
P52
FLUORESCENCE PHOTOSENSITIVE MATERIALS FOR INFORMATION
OPTICAL RECORDING
V.F. Traven, I.V. Ivanov, S.M. Dolotov, D.A. Cheptsov
D. Mendeleev University of Chemical Technology of Russia
In the modern world, computer and information technology continue to develop with increasing
speed, that increases the requirement for higher performance systems that are capable of
preservation, reproduction and processing of information at very high speeds. An actively
developing area, allowing to obtain a carrier with high density recorded information is to
manufacture fluorescent multilayer disks (FMD). Use of the information recording FM-discs is
based on photochemical conversion of compounds that change their fluorescent properties, whether
it is shift of the maximum fluorescence, appearance of fluorescence or its attenuation. [1]
R3
R3
N
h
N
N
N
+H
R1
R2
CH3
H 3C
N
R1
C C l4
CH3
CH3
N
O
H 3C
CH3
+
R2
H
N
CH3
N
O
+
+
CH3
O
OH
O
O
Previously, we have studied new reaction photodehydrogenation 3-pyrazolinylcoumarines and
found it be accompanied by increased acidity [2]. In this report, we consider an application of this
reaction for opening of the lactone form of rhodamine dye. These two reactions are accompanied by
the formation of the fluorophore with a high fluorescence quantum yield and high light resistance.
As we have found both these reactions undergo easily both in organic solvents and in polymer
matrixes. For example, the irradiation of the polymethylmethacrylate film which contain dissolved
pyrazoline, hexachloroethane and lactone of Rhodamine B by light in a wavelength range of 360400 nm leads to the appearance coloration of the film with irradiated areas exhibits fluorescent
properties. We have used these results for optical data recording with fluorescent readout. [3]
1). C. M. Rudzinski, D.G. Nocera, In Optical Sensors and Switches; K.S. Schaze, Ed.; Marcel
Dekker: New York, USA, 2001 (Chap. 1).
2). I.V. Ivanov, S.M. Dolotov, O.I. Kobeleva, T.M. Valova, V. A. Barachevskii, V.F. Traven,
Izv.RAN, Ser.khim. 2012, 2290-2300.
3). V. F. Traven´, S. M. Dolotov, I. V. Ivanov, V. A. Barachevsky, O. I. Kobeleva, T. M. Valova, I.
V. Platonova, A. O. Ait, Patent application no. 3011109935 of March 17, 2011;
163
P53
RING OPENING OF DONOR-ACCEPTOR CYCLOPROPANES WITH
AZIDE ION – STRAIGHTFORWARD ACCESS TO AZA-HETEROCYCLES
K.L. Ivanov, E.V. Villemson, E.M. Budynina, O.A. Ivanova, I.V. Trushkov
Moscow State University, Department of Chemistry, Moscow, Russia
Nucleophilic ring opening of donor-acceptor (DA) cyclopropanes is an efficient approach to various
polyfunctional structures, including natural products and medicines.1-4 Currently, a wide range of
nucleophiles was introduced into reactions with DA cyclopropanes; however, a number of
nucleophilic reagents still remains unexplored. In this research, we have found optimal conditions
for DA cyclopropanes 1 ring opening with azide ion leading to the formation of -azidocarbonyl
compounds 2. Moreover, we developed one-pot process consisting of ring opening/Krapcho
dealkoxycarbonylation which allowed us to achieve a simple approach to the GABA precursors 3.
The concurrent presence of azide function, activated methine or methylene group, EDG and EWG
substituents in compounds 2 and 3 makes them convenient building blocks for the streamlined
synthesis of wide range five- and six-membered N-heterocyclic frameworks which are ubiquitous
structural units of numerous natural and synthetic bioactive molecules. We designed approaches to
pyrrolidones, pyrroles, piperideines, triazolopyridines, tetrazolopyridines, etc. based on simple
synthetic sequences including Staudinger/aza-Wittig cascade or [3+2] cycloaddition as key steps.
These strategies were successfully used in formal syntheses of nicotine and atorvastatin.
1.
2.
3.
4.
Reissig H.-U., Zimmer R., Chem. Rev. 2003, 103, 1151-1196
Carson C.A., Kerr M.A., Chem. Soc. Rev. 2009, 38, 3051-3060
Cavitt M.A., Phun L.H., France S., Chem. Soc. Rev. 2014, 43, 804-818
Schneider T.F., Kaschel J., Werz D.B., Angew. Chem. Int. Ed. 2014, 53, 5504-5523
164
P54
NATURAL GAS HYDRATE FORMATION IN THE PRESENCE OF
SURFACTANTS
I.K. Ivanova1, M.E. Semenov2, I.I. Rozhin2
1 - Ammosov North-Eastern Federal University
2 - Institute of Oil and Gas Problems, Siberian Branch, Russian Academy of Sciences
The aim of the work is determination of the temperature and pressure of formation and
decomposition (melting) of the natural gas hydrate synthesized from natural gas of the Sredneviluy
gas and condensate field (GCF) and distilled water also in the systems based on it: in the presence
of sulfonic of 0,1% by weight, as well as with artificial nucleating agent (sand) by differential
scanning calorimetry.
Fig. 1 Calculated equilibrium conditions of the gas hydrate formation for natural gas of the
Sredneviluy GCF and methane
The experimental data (Fig. 1) are identical to those calculated by the method of E. Dendy Sloan for
the used natural gas hydrate equilibrium conditions. It should be noted that against the background
stands out experimental points obtained by the decomposition of natural gas hydrate, which was
synthesized from a 0,1% solution of sulfonic. Comparing the equilibrium conditions of the
individual components of natural gas, it is found that this point corresponds to the equilibrium
conditions of the methane hydrate. It is known that natural gas hydrates are a mixture of hydrates of
different gases with complex structure. This study suggests the possibility of separation of this
mixture on the hydrates of individual gases. Furthermore, it was found that the use of surfactants
leads to an increased conversion of water into the gas hydrate (> 70%), compared with 2,3% of the
gas hydrate formation in distilled water.
165
P55
CONTROL OF THE REACTION SELECTIVITY IN Pd AND NiCATALYZED HYDROPHOSPHORYLATION OF ALKYNES
J.V. Ivanova1, L.L. Khemchyan1, S.S. Zalesskiy1, V.P. Ananikov1, I.P. Beletskaya2, Z.A. Starikova3
1 - Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia
2 - Lomonosov Moscow State University, Chemistry Department, Moscow, Russia
3 - Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia
Nowadays, transition-metal-mediated carbon-heteroatom (C-E: E=S, Se, Si, P, Te, O) bond
construction has drawn great attention due to well-recognized advantages: high selectivity,
quantitative yields and mild reaction conditions. [1],[2],[3] The study of metal-catalyzed
phosphorus-carbon (P-C) bond formation has led to significant progress in organic synthesis and
established numerous synthetic procedures for the synthesis of new valuable compounds. [1]
We developed two switchable synthetic protocols allowing us to obtain the products of choice via
subtle change in the catalytic system (Scheme 1). The palladium-based catalyst demonstrated high
sensitivity to the number and position of substituent in the aromatic rings of the phosphine ligand.
Application of two different phosphines selectively directed the catalytic reaction either to linear or
branched product formation. [4] The Ni(acac)2/DIBAL-H precatalyst was the first example of
nickel-based system which allowed to synthesize vinylphosphonates, bisphosphonates or
alkyltetraphosphonates without any ligands or solvents. [5],[6] Slight variations of Ni precatalyst
loading routed the selectivity of the hydrophosphorylation reaction. Mechanistic study with ESI-MS
and NMR methods revealed the key nickel intermediates involved into the catalytic cycle. [6]
Scheme 1
[1] V.P. Ananikov, M. Tanaka (Eds.), Hydrofunctionalization, Springer, 2013, Heidelberg. ISBN
978-3-642-33734-5; DOI: 10.1007/978-3-642-33735-2
[2] I.P. Beletskaya, V.P. Ananikov, Chem. Rev., 2011, 111, 1596.
[3] F. Alonso, I.P. Beletskaya, M. Yus, Chem. Rev., 2004, 104, 3079.
[4] V.P. Ananikov, J.V. Ivanova, L.L. Khemchyan, I.P. Beletskaya, Eur. J. Org. Chem., 2012,
3830.
[5] Yu.V. Ivanova, L.L. Khemchyan, S.S. Zalesskii, V.P. Ananikov, I.P. Beletskaya Rus. J. Org.
Chem., 2013, 49, 1099.
[6] L.L. Khemchyan, J.V. Ivanova, S.S. Zalesskiy, V.P. Ananikov, I.P. Beletskaya, Z.A. Starikova,
Adv. Synth. Catal., 2014, 356, 771.
166
P56
Cu-CATALYZED AEROBIC OXIDATIVE TRANSFORMATION OF
KETONE-DERIVED N-TOSYL HYDRAZONES: A NEW ENTRY INTO
ALKYNES
X.-W. Li, W.-Q. Wu, H.-F. Jiang
South China University of Technology, School of Chemistry and Chemical Engineering,
Guangzhou, P. R. China
Alkyne moiety is a fundamental structural element and functional group occurring in various
bioactive molecules, functional materials and natural products.1 Sonogashira reaction and
electrophilic alkynylation2 are the most widely used methods for the construction of alkynes, still,
some formidable challenges remained to be resolved.3 On the other hand, the field of alkyne retrohydration, that is, deprotonation of ketone derivatives for the alkynes synthesis, however, is still in
its infancy. 4
In our continuing efforts toward the development of green chemistry on selective oxidation of
unsaturated hydrocarbons,5 we have developed an efficient copper-catalyzed aerobic
dehydrogenation of ketone-derived N-tosyl hydrazones which were carbene precursors, to the
corresponding alkynes. Further cross-couplings of N-tosyl hydrazones with halides or terminal
alkynes were also performed, delivering to functionalized alkynes or asymmertric diynes. A
mechanism involved aerobic oxidation of Cu-carbene intermediate was proposed for this C-C triple
bond formation.
Reference:
1. Modern Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH, Weinheim, Germany,
1995.
2. Dudnik, A. S.; Gevorgyan, V. Angew. Chem. Int. Ed. 2010, 49, 2096.
3. Negishi, E.; Anastasia, L. Chem. Rev. 2003, 103, 1979.
4. Negishi, E.; King, A. O.; Klima, W. L.; Patterson, W.; Silveira, A. J. Org. Chem. 1980, 45,
2526.
5. Wu, W.; Jiang, H. Acc. Chem. Res. 2012, 45, 1736.
167
P57
[Co]-СATALYZED [6+2]-CYCLOADDITION OF 1,2-DIENES TO 1,3,5,7CYCLOOCTATETRAENE
V.A. Dyakonov1, G.N. Kadikova1, G.F. Gazizullina2, U.M. Dzhemilev1
1 - Federal State Institution of Science Institute of Petrochemistry and Catalysis, Russian Academy
of Sciences; Laboratory catalytic Synthesys; Ufa; Russia
2 - Ufa State University of Economics and Service; Ufa; Russia
Eight-membered carbocycles are found in many natural compounds exhibiting high biological
activity [1]. The catalytic cycloaddition based on 1,3,5,7-cyclooctatetraene (COT) are an effective
method for the synthesis of such carbocycles [2]. [Co]-Catalyzed cyclodimerization of COT with
alkynes leading to the formation of bicyclo[4.2.2]deca-2,4,7,9-tetraenes 1 [3].
R
C o I 2 /d p p e /Z n /Z n I 2 ,
4 0 o C , C 2 H 4 C l2
R
1
It should be noted that in literature have no examples of catalytic codimerization of 1,3,5,7cyclooctatetraene with 1,2-dienes. In the development of this work and our ongoing research [4a,b]
we carried out [6π+2π]-cycloaddition of COT with 1,2-dienes in the presence of 10 mol%
CoI2/dppe/Zn/ZnI2 (C2H4Cl2, 40 ° C, 20 h). The corresponding bicyclo[4.2.2]deca-2,4,7-trienes 2
were obtained in high yields.
R
C o I 2 /d p p e /Z n /Z n I 2 ,
4 0 o C , C 2 H 4 C l2
R = P h , A lk
R
2
This work was performed under financial support from the Russian Foundation for Basic Research
(Grant 13-03-00167 and Grant of RF President (Sci. Sh. – 2136.2014.3)).
1. Plemenkov V.V. Introduction to the chemistry of natural compounds. Kazan, 2001, 376 p.
2. Yu Z.X, Wang Y., Wang Y. Transition-metal-catalyzed cycloadditions for the synthesis of eightmembered carbocycles, Chem. Asian J., 2010, 1072-1088.
3. Achard M., Mosrin M., Tenaglia A., Buono G. Cobalt (ΙΙ)-Catalyzed [6+2] Cycloadditions of
Cyclooctatetra(tri)ene with Alkynes, J.Org.Chem, 2006, 71, 2907 -2910.
4. a) Dyakonov V.A., Kadikova G.N., Dzhemilev U.M. Ti-catalyzed [6π +2 π]-cycloadditions of
allenes with 1,3,5-cycloheptatriene, Tetrahedron Lett., 2011, 52, 2780-2782; b) Dzhemilev U.M.,
Kadikova G.N., Kolokoltsev D.I., Dyakonov V.A. Catalytic [6π+2π]-cycloaddition of alkynes,
1,2- and 1,3-dienes to 1,3,5-cycloheptatrienes involving Ti complexes, Tetrahedron, 2013 , 69,
4609-4611.
168
P58
MOBILE NANODEFECTS AS COMPLEXING AGENTS IN SOLID PHASE
CHEMISTRY
A.M. Kaplan, N.I. Chekunaev
N.N.Semenov Institute of Chemical Physics, Russian Academy of Sciences
Put forward by one of the authors, the idea about the possible role of mobile nanodefects as
complexing agents, allowed to explain for the first time a number of non-trivial effects of solidphase chemistry. These are: 1. the effect of greatly acceleration of catalytic processes induced by
high energy impacts on heterogeneous catalysts [1]; 2. the phenomena of "freezing" of polymer
chains at constant temperatures and "reanimation" of such chains at temperatures increasing of
investigated samples in solids [2]; 3. the effect of exceeding by several orders of the rate of
affiliation of monomer molecules to the active centers in glass monomers samples compared to
crystalline samples of the monomer [3]; 4. the phenomenon of the abnormal logarithmic time
dependence of the polymer yield for unterminated solid-state polymerization at low conversions [4].
In contrast to gas and liquid phases, very low orientation mobility of microparticles in solid phase
frequently does not allow to perform chemical interaction even particles of reagents which are in
contact with each other for prolonged time. This effect is a consequence of unacceptable for
chemical interaction starting mutual orientation of the particles and impossibility to improve the
situation at insufficient space close to them. Furthermore, structural nanodefects (mobile vacancies,
polyvacancies, dislocations, nanoincontinuity, etc) present in the real solid bodies may, in case of
their sufficient mobility, lead to pair of potentially chemically capable, but unreacting due to
orientational immobility of adjacent reagents particles, in quite dense areas of solid bodies
sufficient free space. Remobing by this the steric barrier for the interactions of such particles.
Consequently, as it was for the first time mention by the presenter, real (‘living’) active center (A*)
of solid phase reactions should be considered not the experimentally detectable traditional active
centers (A) (radical and ions), but a peculiar complex of such centers with the carrier of excess of
volume — with mobile nanodefects. The concentration of [A*]<<[A]. It should be pointed out the
special role of mobility of nanodefects in formation of real cative centers A*. In case of presence of
in the system of only motionless nanodefects, “chemical” diffusion leads in time to the removal of
reacting particles from such defects, turming these particles to inactive state. In heterogenous
catalysis this effect is similar to the effect of catalyst poisoning. Movable nanodefects which
activated during some time a group of reagent particles, move to another such group, and also
activate it. This process of activation of chemical process takes places until meeting of moving
nanodefects, leading to sticking of defects and decrease of their concentration. Based on concept of
moving nanodefects with excessive free volume as complexing agents, authors using computer
calculations in papers [1-4] explained the effects previously considered anomalous mentioned
above.
1. A.M.Kaplan, V.V.Lunin, N.I.Chekunaev. Book of abstracts of VII Voevodsky conference
«Physics and Chemistry of elementary chemical processes». P. 191-192. Chernogolovka. 2007.
2. A.M. Kaplan, N.I. Chekunaev. Doklady Physical Chemistry, Vol. 425, Part 1, pp. 51-53, 2009.
3. A.M. Kaplan, N.I. Chekunaev. Russian Chemical Bulletin. No. 8, pp. 677-683. 2009.
4. A.M. Kaplan, N.I. Chekunaev. Polymer Science. Series B, Vol. 52, No. 1-2, pp. 57-62, 2010.
169
P59
SYNTHESIS OF OLIGOSACCHARIDE FRAGMENTS OF CANDIDA
ALBICANS MANNAN CORRESPONDING TO ANTIGENIC FACTOR 6
A.A. Karelin, Y.E. Tsvetkov, N.E. Nifantiev
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Laboratory of
Glycoconjugate Chemistry, Moscow, Russia
The yeast-like fungi of the genus Candida are opportunistic pathogenic microorganisms capable of
causing severe infections in immunocompromised patients. The main surface antigen of Candida
responsible for its antigenic specificity is mannan, which represents the carbohydrate part of the cell
wall mannoprotein. The determinants of antigenic factor 6 are represented by several β-D-Man(1→2)-residues attached to short α-(1→2)-linked chains.
Here we report synthesis of oligosaccharides 1 and 2 containing two and three β-linked residues.
The presence of the amino group in the aglycones of the synthetic oligosaccharides allows their
subsequent covalent binding to high-molecular carriers and labels of various types
We utilized a convergent approach based on glycosylation of known α-(1→2)-linked mannosyl
acceptor with β-(1→2)-linked donors.
The preparation of required donors was started from compound 3. The thiomannoside was
transformed into sulfoxide 4. Then these monosaccharides were coupled to give required
disaccharide donor. Here we used the fact that conditions of sulfoxide activation don’t affect
thioglycosides. Oxidation of dimanosyl donor 5 followed by glycosylation of 3 allowed obtaining
trisaccharide donor 7. Glycosylation of α-(1→2)-linked mannosyl acceptor with donors 5 and 7 and
subsequent removal of protecting groups gave target olygomannosides 1 and 2.
Acknowledgments
This work was supported by the Russian Foundation for Basic Research under grant 14-03-31583
170
P60
NANOSTRUCTURED NICKEL ORGANOSULFIDES: SYNTHESIS,
CHARACTERIZATION AND APPLICATION IN THE CATALYTIC
CARBON-SULFUR BOND FORMATION REACTION
A.S. Kashin, V.P. Ananikov
N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia
Over the last decades nanostructured metal chalcogenides have made an outstanding contribution to
the nanotechnology, microelectronics, optics and material science. However their application in
organic synthesis and catalysis remains largely unexplored [1].
In our work we focused on the nickel organosulfides – [Ni(SAr)2]n. These nanostructured nickel
complex salts can be easily prepared by the reaction between nickel acetylacetonate and aryl thiols.
Rapid ligand substitution accompanied with the self-organization in solution leads to formation of
polymeric structures, where nickel atoms are linked by μ2-SAr groups. Tuning of the reaction
conditions or changing of the substituent in the aromatic ring of thiol allows to generate [Ni(SAr) 2]n
particles of various shapes and sizes (Figure 1).
Figure 1. FE-SEM images of [Ni(SAr)2]n particles, Ar = Ph (A), p-BrPh (B).
We have demonstrated that synthesized nickel aryl sulfides can be utilized as a source of SAr
groups for the carbon-sulfur bond formation in the cross-coupling reaction with aryl halides [2].
Reaction in the presence of palladium- or copper-based catalytic system results in the diaryl sulfides
formation with the yield up to 95% (Scheme 1).
Scheme 1. Catalytic C-S bond formation reaction between nickel organosulfides and aryl halides.
A unique effect of morphology control of the SAr group donor reactivity in cross-coupling reaction
was found. Mechanistic studies have shown that cross-coupling reaction with Cu catalyst proceeds
in the liquid phase and involves leaching, whereas the same reaction with Pd catalyst is more
complex and may involve both – homogeneous and heterogeneous pathways.
[1] V.P. Ananikov, I.P. Beletskaya, Dalton Trans. 2011, 40, 4011.
[2] A.S. Kashin, V.P. Ananikov, Top. Catal. 2013, 56, 1246.
171
P61
SYNTHESIS OF DERIVATIVES OF 6-ACETYL-2-CYCLOHEXENONE AND
THEIR BORON CHELATE COMPLEXES
D.S. Khachatryan1, I.I. Boyko2, A.A. Vardapetyan1, A.L. Razinov1, K.R. Matevosyan3
1 - FGU "IREA", Moscow, Russia
2 - ООО "TEHNOLOG", Pereslavl-Zalessky, Russia
3 – DI Mendeleev RHTU, Moscow, Russia
In some cases, reactions of enolates obtained using conventional basic reagents (alcoholates,
amides, metal hydrides) afford products in very low yields1,2. In the late 70's we first succesfully
used patassium carbonate in Michael reaction for the synthesis in preparative quantities of
derivatives of 2-cyclohexenone 2-4 – synthons for construction of physisologically active molecules,
including steroids1.
The present work follows the studies in the field of synthesis of new derivatives of 2-cyclohexenone
by Michael reaction in the presence of patassium carbonate. Of special interest are derivatives of 2cyclohexenone containing acetyl substituent in position 6 – analogues of 1,3-diketones which can
complex transition and rear yearth metals 5-7.
We studied prepartion of 3,5-disubstituted 6-acetyl-2-cyclohexenones, based on cyclocondensation
reaction of acetylacetone (1) with α,β-unsaturated ketones 2а-h in the presence of catalytic amount
of patassium carbonate at reflux in different solvents.
O
O
+
R
1
R
Me
Me
R
O
1
O
Me
2 a -h
R
1
R
Me
O
Me
1
R
O
3 a -h
O
O
4 a -h
а R=MeOC6H4CH=CH; R1=MeOC6H4; b R=R1=Ph; c R=2-тиенил, R1=Ph;
d R=2,4-Cl2C6H3CH=CH, R1=BuOC6H4; e R=4-BuOC6H4CH=CH; R1=4-BuOC6H4;
f R=4-AmOC6H4CH=CH; R1=4-AmOC6H4; g R=4-lC6H4CH=CH; R1=4-ClC6H4;
h R=4-MeC6H4CH=CH;R1=4-MeC6H4
In 1Н NMR spectra of all diketones 4a-h, the doubling of all expected signals is observed that, as
known7, is due to keto-enol tautomerism, i.e. 6-acetyl-2-cyclohexenones behave in solution as
classic 1,3-diketones.
Based on these data, the chelating ability of compounds 4a-h was evaluated. It was shown that they
can form chelate complexes with boron – 1,3-dioxaborines, which possess photosensibilizing
properties5, as well as (with compound 4b as an example) complexes with metals (Сu2+, Ni2+, Со2+,
Еu3+) 4,6.
1 E.D. Bergmann, D.Ginsburg, R.Pappo, in Organic Reactions, v.10, Wiley, New York, 1959.
2 N.M.Morlyan, D.S. Khachatryan, Sh.O. Badanyan, Arm. Chem. J. 1978, 31 (2) 866.
3 D.S. Khachatryan, A.A. Vardapetyan, G.A. Panossian, R.G. Mirzoyan, N.M. Morlyan, ZhOrH. 1990, 26
(10), 2092.
4 D.S. Khachatryan, A.A. Vardapetyan, V.N. Tkachenko, N.M. Morlyan, Proc. Conf., «III All-Union
Conference on Chemical reagents", Ashgabat, 1989, p 107.
5 I.I. Boyko, T.I. Boyko, A.A. Vardapetyan, G.V. Nowicka, D.S. Khachatryan, N.M. Morlyan and K.K.
Koshelev. A.s.1704446 USSR; Bull. Izobr., 2000, 9.
6. V.I.Zelenov, Russian J.Gen.Chem. 2009.79 (1), 142.
7. J.K.F.Geirsson, A.D.Gudmundsdottir, Synthesis, 1990, 11, 993.
172
P62
TRITERPENOID SAPONINS FROM THE ROOTS OF
ACANTHOPHYLLUM GYPSOPHILOIDES REGEL AS POTENTIAL
IMMUNE-MODULATING TOOLS FOR DENDRITIC VACCINE DESIGN
E.A. Khatuntseva1, V.M. Men’shov1, A.S. Shashkov1, Y.E. Tsvetkov1, R.N. Stepanenko2, R. Ya.
Vlasenko2, E.E. Shults3, G.A. Tolstikov3, T.G. Tolstikova3, D.S. Baev3, V.A. Kaledin4, N.A.
Popova4, V.P. Nikolin4, P.P. Laktionov5, A.V. Cherepanova5, T.V. Kulakovskaya6, E.V.
Kulakovskaya6, N.E. Nifantiev1
1 - N. D. Zelinsky Institute of Organic Chemistry, RAS, Leninsky pr. 47, Moscow, RF
2 - Institute of Immunology, Ministry of Health and Social Development of RF, Kashirskoe Ch.,
24/2, Moscow, RF
3 - N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of RAS, pr. Acad.
Lavrent’eva, 9, Novosibirsk, RF
4 - Institute of Cytology and Genetics Siberian Branch of the RAS, 10 pr. Acad. Lavrent’eva,
Novosibirsk, RF
5 - Institute of Chemical Biology and Fundamental Medicine, Siberian Branch of the RAS, 8 pr.
Acad. Lavrent’eva, Novosibirsk, RF
6 - G. K. Skryabin Institute of Biochemistry and Physiology of Microorganisms, RAS, Pushchino
Despite significant effort, the development of effective vaccines inducing strong and durable T-cell
responses against cancer cells has remained a challenge. It is anticipated that the main target of
vaccination are dendritic cells, the principal antigen presenting cells, whose main function is to
identify exogenous structures and present them to naïve CD4+ and CD8+ T cells in lymph nodes. A
current strategy to enhance the effectiveness of vaccination is to deliver antigens directly to
dendritic cells, which are readily accessible within the well-established in vitro procedure. Anticancer dendritic vaccines are intended to activate cytotoxic antigen-specific CD8+ T cells, which are
activated via complexes with MHC class I molecules of DCs, with the only possibility of
exogenous antigen presentation on those to be done by cross-presentation. This process includes
translocation of the antigen from the endosome to the cytosol and is known to be efficiently
promoted by saponins, which are part of saponin-based adjuvants QS21 and ISCOMATRIX.
Amphiphilic nature of most saponins enables the formation of nano-sized micelles, and among
them immune-stimulating complexes (ISCOM), which are currently used as adjuvant systems.
These particles are known to be readily engulfed by DCs and the optimal uptake of this type of
vesicles by DCs was reported to be achieved when particle size is 0.5 – 5 μm, which corresponds to
conventional size of saponin-based micelles in water solutions.
The objective of the present work was to isolate new individual saponins from readily available
routs of Acanthophyllum gypsophiloides with the view to further investigation of their vesicle
formation potential and in vitro effect of saponin-containing ISCOM s on dendritic cells.
Two new triterpenoid saponins 1 and 2 were isolated from the methanol
extract of the roots of Acanthophyllum gypsophiloides Regel. These saponins have quillaic acid or gypsogenin moieties as aglycon and both bear
similar sets of two oligosaccharide chains, which are trisaccharide -LAra-(1→3)-[ -D-Gal-(1→2)]- -D-GlcA and pentasaccharide -D-Xyl(1→3)- -D-Xyl-(1→3)- -L-Rha-(1 2)-[ -D-Qui-(1→4)]- -D-Fuc
connected to C-28. The structures were elucidated by the combination of
1 R = OH; 2 R = H
mass spectrometry and 2D NMR spectroscopy methods.
Reference: E.A. Khatuntseva et al., Beilstein J Org Chem. 2012,8:763-75.
173
P63
NMR SPECTROSCOPY AND ESI-MS AS EFFECTIVE RAPID METHODS
FOR MONITORING BIOMASS CONVERSION INTO 5-HMF IN IONIC
LIQUIDS
E.A. Khokhlova, V.V. Kachala, V.P. Ananikov
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Unprecedented selectivity for biomass and cellulose conversion to 5-HMF has opened outstanding
opportunities for sustainable chemical industry. 5-HMF was identified as a "platform chemical" for
production of biofuels, solvents, resins, liquid alkanes (C7 - C15), and monomers for plastics.
However, in spite of complete conversion, more detailed studies have shown moderate product
yields (40-60%), and later, formation of by-products (humins) has been identified. The main
stumbling block to studying cellulose processing in ionic liquids is the absence of an analytic tool
for monitoring reaction yields in ionic liquids.[1]
Our research has been focused on real-time carbohydrate conversion monitoring using a new NMR
based approach for quantitative measurements. A practical application of the developed approach
was demonstrated directly in the NMR tube. Our latest study revealed the ways to characterize
molecular transformations in IL systems and to detect reaction intermediates using a special reactor
that eliminates microheterogeneity.[2] Transformation of carbohydrates to 5-HMF with various
promoters was investigated and discrepancy between conversions and yields was observed. Highquality NMR spectra suitable for integration of individual signals were measured after removing the
intrinsic heterogeneity of ionic liquid samples below the spectroscopic detection level.
Moreover, we have disclosed a new opportunity of using the MS2 mode in reaction monitoring
frameworks that make it possible to obtain both qualitative and quantitative information. A
combined use of the developed NMR and mass spectrometry approaches for analyzing components
of IL solutions will expand the frames of promising chemistry in ILs.
[1] V.P.Ananikov, Chem. Rev. 2011, 111, 418.
[2] E.A.Khokhlova, V.V.Kachala, V.P.Ananikov. ChemSusChem, 2012, 5, 783.
174
P64
Rh(III) CATALYZED SYNTHESIS OF ISOQUINOLINE DERIVATIVES BY
ANNULATION OF BENZYLAMINES WITH ALKYNES
D.-S. Kim, C.-H. Jun
Yonsei University, Department of Chemistry, Seoul, Korea
Rh(III)-catalyzed C-H bond cleavage is one of efficient ways to make N-heterocyclic compounds.1
In particular, ortho-alkyl- or alkenylation provides an efficient synthetic method for preparing
ortho-substituted aromatic ketones.2 During the course of our studies on the Rh(III)-catalyzed Nannulation reaction, we found synthetic method of pyridine derivatives from primary allylamines
with alkynes.3 In this poster, we report a new protocol for the preparation of isoquinoline from
benzylamine and internal alkyne using Rh(III)-catalyst with Cu(II) as an oxidizing agent. For
example, the N-heterocyclic annulation reaction of 2-methoxybenzylamine with 4-octyne was
carried out at 100 oC for 4 hours in the presence of [Cp*RhCl2]2 (2.5 mol% [Rh]) and
Cu(OAc)2.H2O to produce corresponding pyridine in 92% yield. The proposed mechanism of this
annulation reaction is also discussed.4
1. Song, G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, 3651-3678.
2. Murai, S.; Kakiuchi, F; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M. Chatani, N. Nature,
1993, 366, 529-531.
3. Kim, D.-S.; Park, J.-W.; Jun, C.-H. Chem. Commun. 2012, 48, 11334-11336.
4. Kim, D.-S.; Park, J.-W.; Jun, C.-H. Adv. Synth. Catal. 2013, 355, 2667-2679.
175
P65
A NOVEL BRANCHED MONOSACCHARIDE, 3,6-DIDEOXY-4-C-[(S)-1,2DIHYDROXYETHYL]-D-XYLO-HEXOSE, FROM A POLYSACCHARIDE
OF A BACTERIUM OF THE GENUS PHOTORHABDUS
N.P. Arbatsky1, A.S. Shashkov1, N.A. Kirsheva2, A.N. Kondakova1, R.Z. Shaikhutdinova2, S.A.
Ivanov2, A.P. Anisimov2, Y.A. Knirel1
1 - N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
2 - State Research Center for Applied Microbiology and Biotechnology, Obolensk, Moscow Region,
Russia
The genus Photorhabdus from the family Enterobacteriaceae includes three species of
entomopathogenic bioluminescent bacteria Photorhabdus temperata, Photorhabdus luminescens,
and Photorhabdus asymbiotica. They all have a mutualistic relationship with entomophagous
nematodes from the family Heterorhabditis. These bacteria synthesize an S-form
lipopolysaccharide, which consists of lipid A, core oligosaccharide, and O-specific polysaccharide
(O-antigen) and is important for both pathogenicity and symbiosis. Recently, aiming at creation of
the chemical basis for classification of Photorhabdus species, structures of the O-polysaccharides of
representatives of P. asymbiotica subsp. asymbiotica and subsp. australis1 and P. luminescens
subsp. laumondii2 have been elucidated. In this work, we established the O-polysaccharide structure
of P. temperata subsp. temperata XlNachT and identified a novel branched monosaccharide as its
component.
The O-polysaccharide was obtained by mild acid hydrolysis of the lipopolysaccharide isolated from
bacterial cells by phenol-water extraction. In addition to monosaccharides that are rather common in
nature (glucose, mannose, galactose, and N-acetylgalactosamine), sugar analysis of the
O-polysaccharide revealed a branched octose called photorhabdose. The new sugar was isolated as
a 1,2’-anhydro furanose derivative by reversed-phase HPLC after full acid hydrolysis of the
O-polysaccharide (Scheme), and its structure as 3,6-dideoxy-4-C-[(S)-1’,2’-dihydroxyethyl]-D-xylohexose was determined by one- and two-dimensional 1H and 13C NMR spectroscopy.
Photorhabdose has not been hitherto found in nature and differs from the known branched octoses,
3,6-dideoxy-4-C-[(S)- and (R)-1-hydroxyethyl]-D-xylo-hexoses (yersinioses A and B, respectively),
in deoxygenatation of the terminal carbon (C-2’) of the side chain.
Scheme. Isolation of photorhabdose (Sug) by full acid hydrolysis of the O-polysaccharide. Arrows
indicate H,H correlations observed in the NOESY spectrum.
1. Kondakova, A. N.; Kirsheva, N. A.; Shashkov, A. S.; Shaikhutdinova, R. Z.; Arbatsky, N. P.;
Ivanov, S. A.; Anisimov, A. P.; Knirel, Y. A. Carbohydr. Res. 2011, 346, 1951-1955.
2. Kondakova, A. N.; Kirsheva, N. A.; Shashkov, A. S.; Shaikhutdinova, R. Z.; Ivanov, S. A.;
Anisimov, A. P.; Knirel, Y. A. Carbohydr. Res. 2012, 351, 134-137.
176
P66
EVOLUTION AND INTERLAYER DYNAMICS OF ACTIVE SITES OF
PROMOTED TRANSITION METAL SULFIDE CATALYSTS UNDER
HYDRODESULFURIZATION CONDITIONS
V.M. Kogan1, P.A. Nikulshin2, N.N. Rozhdestvenskaya1
1 - N.D. Zelinsky Institute of Organic Chemistry, RAS, Laboratory of catalysis by trasition metals
and their compounds, Moscow, Russia
2 - Samara State Technical University, Samara, Russia
According to the suggested dynamic model [1], neighboring layers of the multilayered MoS 2
crystallite exchange sulfur between Mo- and S-edges placed one under another in the course of
permanent reduction–sulfidation processes under hydrogen atmosphere. When the sulfur atoms
bonded to Co atoms leave the reduced edge of the layer, the atoms of the promoter also move along
the sulfur atoms from one layer to an adjacent layer of higher sulfidation state. Then the process
reverses. Such oscillations occur until the sulfur organic compound adsorbs on the vacancy on the
reduced edge. The frequency of the oscillations determines catalytic activity of the CoMoS slab.
Thiophene adsorption makes transfer of a promoter to the neighboring slab improbable because the
electron density of thiophene sulfur compensates the extra positive charge on the Mo atom appeared
after H2S removal. When thiophene adsorbs on the vacancy of the CoMoS site the proton linked to
Co moves to the SH group of the neighboring layer forming the H2S which desorbs from this layer
and new vacancy is formed. This model explains the reasons of the electron transfer from atom of
promoter to Mo and different locations of the active sites responsible for hydrogenation and
desulfurization on a promoted Mo-sulfide slab. A method to evaluate the efficiency of CoMoS
catalysts for HDS of various types of crudes has been developed. Now these findings obtain their
explanations within the developed dynamic model (Fig. 1).
Fig. 1. Dynamic model of
transformations of the active
sites of promoted TMS
catalysts in the course of
thiophene HDS.
The suggested model gives a basis to develop criteria to evaluate the efficiency of the catalyst
activity in hydrotreating of various types of crude oil.
1. V.M. Kogan, P.A. Nikulshin, N.N. Rozhdestvenskaya, Fuel 100 (2012) 2.
177
P67
THE CONCEPT OF INTERLAYER DYNAMICS AND THE MECHANISMS
OF HDS AND ALCOHOL SYNTHESIS ON THE ACTIVE SITES OF
PROMOTED TMS CATALYSTS
V.M. Kogan1, P.A. Nikulshin2, V.S. Dorokhov1
1 - N.D. Zelinsky Institute of Organic Chemistry, RAS, Laboratory of catalysis by trasition metals
and their compounds, Moscow, Russia
2 - Samara State Technical University, Samara, Russia
A new mechanistic model for molybdenum sulfide catalysts with cobalt and nickel promoters under
hydrodesulfurization (HDS) reaction conditions is proposed that includes dynamic migration of
sulfur and promoter atoms between adjacent sulfide layers [1,2]. These migrations are caused by
heterolytic dissociation of gas-phase hydrogen and formation of hydride hydrogen on a promoter
atom. Hydride hydrogen adsorbed on a promoter induces electron density transfer from the bonding
promoter to Mo, changing its catalytic activity. Adsorbed hydrogen induces migration of sulfur and
promoter atoms between adjacent clusters. This dynamic migration causes transformation of
‘‘rapid’’ into ‘‘slow’’ sites and vice versa and, therefore, influences catalytic activity. Migration of
Co or Ni promoter atoms to Mo sites on the rim is more likely than to Mo sites on the edge of
Co(Ni)MoS layers because the former can accept promoter atoms from both upper and lower layers.
A method to evaluate the efficiency of CoMoS catalysts for HDS of various types of crudes has
been developed. The proposed model provides crutial information for rational design of improved
hydrotreating catalysts and selection of preferred catalytic reaction conditions for various types of
hydrocarbon feedstock via optimization of the density and ratio of ‘‘rapid’’ and ‘‘slow’’ catalyst
active sites.
Application of the dynamic model to the investigation of the mechanism of the mixed alcohol
synthesis (MAS) over TMS catalysts modified by potassium gives us ground to assume that the
reaction of alcohol formation from synthesis gas proceeds on almost the same types of active sites
as it takes place for HDS. Unlike HDS sites, responsible for hydrogenolysis of CS bond, the MAS
sites, responsible for alcohol formation, are modified by potassium (Fig. 1).
5%K
10 % K
15 % K
Fig. 1. TEM images of the CoMoS/Al2O3 catalyst modified by 5, 10 and 15 % of K and the models of
intercalation of K+ ions between the layers of the MoS2 crystallites.
The TEM data witness that K addition increases stacking number. The catalytic examinations show
that potassium promotes alcohol yield. Basing on these data we suppose that K ions intercalate
between neighbouring MoS2 layers affecting the active phase morphology and (AS)’s selectivity in
MAS. The Co-promoted catalyst is more selective to alcohols than the non-promoted one.
Promoting activity Co in MAS and HDS lets us suppose that the nature of the active sites operating
in both reactions is similar.
[1] V.M. Kogan, P.A. Nikulshin, Catal. Today 149 (2010) 224.
[2] V.M. Kogan, P.A. Nikulshin, N.N. Rozhdestvenskaya, Fuel 100 (2012) 2.
[3] V.M. Kogan, N.N. Rozhdestvenskaya, I.K. Korshevets, Appl. Catal. A: Gen. 234 (2002) 207.
178
P68
RELATIONSHIP BETWEEN ACTIVE PHASE MORPHOLOGY AND
CATALYTIC PROPERTIES OF THE CARBON-ALUMINA-SUPPORTED
Co(Ni)Mo CATALYSTS IN HDS AND HYD REACTIONS
P.A. Nikulshin1, V.A. Salnikov1, A.A. Mozhaev1, P.P. Minaev1, V.M. Kogan2, A.A. Pimerzin1
1 - Samara State Technical University, Samara, Russia
2 - N.D. Zelinsky Institute of Organic Chemistry, RAS, Laboratory of catalysis by trasition metals
and their compounds, Moscow, Russia
Effects of activated carbon of a carbon-coated alumina (CCA) support and active phase morphology
of transition metal sulfide (TMS) catalysts in hydrotreatment (HDT) of S-containing compounds
were studied. The catalysts were synthesized from Anderson-type heteropolycompounds and
characterized with multiple methods: X-ray powder diffraction, N2 physisorption, temperatureprogrammed desorption of ammonia, pyridine-adsorbed Fourier transform infrared spectroscopy,
H2 temperature programmed reduction, and high resolution transmission electron microscopy. The
catalysts were tested in hydrodesulfurization (HDS) of thiophene, dibenzothiophene and HDT of
diesel. To interpret the obtained results, we used an interlayer dynamics concept developed recently
[1]. The TPR measurements indicate hydrogen uptake by the C-coated support at reaction
temperatures. It witnesses that CCA accumulates gas-phase hydrogen and could be a source of
hydrogen for HDT reactions. Carbon affects active phase morphology: changing the carbon content
it is possible to vary a stacking number/linear size ratio of the active phase particles and, thereby, to
control hydrogenation to direct desulfurization (HYD/DDS) selectivity (Fig. 1).
(a)
(b)
Var3
3
2’
)
0.7
0.6
0.5
0.4
0.3
SHYD/DS
0.8
1 - 1’
3 - 3’
2 - 2’
3’
0.7
0.6
0.5
0.4
0.3
g
in
ck
r
be
m
nu
L
Var2
er
mb
sta
ta
es
3.0
3.4 3.2
3.8 3.6
th, nm
4.2 4.0
g
n
le
4.4
age
4.6
Aver
1
ge
ag
cki
ng
er
3.2
3.0
2.8
2.6
2.4
4’
1’
2.2
4.6
2.0
4.4
4.2
Ave
1.8
rag 4.0 3.8
e le
1.6
ngth 3.6
1.4
, nm 3.4
3.2
3.0 1.2
nu
4
Av
N
4 - 4’
0.9
N
(c)
e ra
2
1
10 (s
2.6
2.4
2.4
1.8
2.2
1.5
2.0
0.6
1.8
1.6
1.4
1.2
1.0
0.8
0.6
3.2
3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
Av
4
TOF
L
В
Var1
Fig. 1. 3D dependences of TOF number (a) and HYD/DDS selectivity (b) in DBT HDS on average
length and average stacking number of Co(Ni)MoS2 particles in the catalysts; schematic
visualization of the morphology of promoted MoS2 slabs variation depending on the number of the
active sites on the edges and rims of the slabs (c).
An increase in the average linear size of the slab leads to a drop of HDS and HYD activities. The
longer layers in the slabs, the fewer solid angles are, and so the higher the effect of the support. On
the contrary, in the multilayered structure the support effect diminishes. The observed high
HYD/DDS selectivity of the catalysts synthesized from AHM and nickel nitrate may be caused by
low edge surface Ni on the MoS2 slab which should also form the unpromoted Mo-sites responsible
for the HYD reactions on the edges. The results suggest that the catalytic activity in HDS and HYD
reactions depends on the shape of crystallites of the active phase. The results are interpreted using
recently proposed concepts of interlayer dynamics. These concepts are helpful in establishing
structure-activity relations for TMS.
1. V.M. Kogan, P.A. Nikulshin, N.N. Rozhdestvenskaya, Fuel 100 (2012) 2.
179
P69
GENESIS OF HDT CATALYSTS PREPARED WITH THE USE OF
Co2Mo10HPA AND COBALT CITRATE: STUDY OF THEIR GAS AND
LIQUID PHASE SULFIDATION
P.A. Nikulshin1, A.V. Mozhaev1, K.I. Maslakov2, A.A. Pimerzin1, V.M. Kogan3
1 - Samara State Technical University, Samara, Russia
2 - M.V. Lomonosov Moscow State University, Chemistry Department, Moscow, Russia
3 - N.D. Zelinsky Institute of Organic Chemistry, RAS, Laboratory of catalysis by trasition metals
and their compounds, Moscow, Russia
Production of clean fuels with less than 10 ppm sulfur content is one of the most important and
claiming the attention problem in recent petroleum refinery. The countermeasures for the ultra deep
desulfurization are to apply novel highly active catalysts, and to optimize the operation condition of
the hydrodesulfurization (HDS) process. The development and application of more active and stable
catalysts could enhance the productivity and improve the product quality without negative impacts
on capital investment.
Genesis of alumina supported hydrotreating (HDT) catalysts prepared with the use of
decamolybdodicobaltate heteropolyanion (Co2Mo10HPA) and cobalt citrate during their sulfidation
processes and deactivation in diesel HDT has been investigated. The sulfidation stage was studied
for two procedures: gas phase sulfidation by H2S/H2 and liquid phase treatment by a mixture of
dimethyldisulfide in diesel at various temperatures and durations. The catalysts have been studied
by N2 adsorption, thermogravimetric analysis, X-ray photoelectron spectroscopy and highresolution transmission electron microscopy methods. The catalysts were tested in HDT of mixture
of 70 wt.% straight run gas oil with 16 wt.% light cycle oil and 14 wt.% light coker gas oil.
Mechanisms of the active phase formation in the course of gas and liquid phase sulfidation
processes have been established (Fig. 1).
Fig. 1. CoMoS phase formation
mechanisms during gas and liquid phase
sulfidation
of
the
Co3(CA)4.5Co2Mo10/Al2O3 catalyst (S – average
stacking number, L – average length
were found from TEM; Co content in
CoMoS phase and (Co/Mo)slab were
found by XPS).
It was found that gas phase sulfidation led to formation of the CoMoS active phase with higher
cobalt content comparing to liquid sulfidation of the catalyst and initial activity of the gas phase
treated catalysts in diesel HDT was also higher than catalysts subjected to liquid sulfidation.
Catalytic examination after accelerated deactivation conditions showed that the liquid phase
sulfided sample was more resistant to the deactivation. Probably it is due to stabilization of active
phase particles by coke formed intensively during liquid phase sulfidation. In liquid phase
sulfidation, both metals are sulfided simultaneously with the formation of nuclei of CoMoS phase II
type at low temperature (2300C). At high temperature (340 0C) the increase of particle size of
CoMoS phase is occurred.
180
P70
SYNTHESIS OF HEPTASACCHARIDE FRAGMENT CORRESPONDING
TO α-(1-3)-GLUCAN OF ASPERGILLUS FUMIGATUS
M.V. Orekhova, B.S. Komarova, N.E. Nifantiev
Laboratory of Glycoconjugate Chemistry,N.D. Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences Leninsky Prospect 47, 119991 Moscow, Russia
For immunocompromised individuals Aspergillus fumigatus is the most important and life
threatening pathogen. [1] In the cell walls of this ubiquitous fungus -(1→3)-glucan constitutes the
main polysaccharide, [2] which forms biofilms and is a cause of permanent infection. [3] Previously
a synthesis of spacer armed -(1→3)-pentaglucoside conjugates with BSA and biotin was achieved.
These derivatives were used for obtaining and characterization of antibodies recognizing α-(1→3)glucan, which were used for tracing A. fumigatus cells. However for the final goal of the project, the
development of a vaccine against A. fumigatus, the five glucosyl units in the chain is not enough.
In the present report a synthesis of 3-aminopropyl -(1→3)-pentaglucoside 1 (Scheme) is
described. The success of convergent scheme toward the target compound relied on the use of
disaccharide 2 which was modified by orthogonal levulinoyl (Lev) and p-methoxyphenyl (pMP)
groups. The ability to remove Lev and pMP groups independently made it possible to prepare
disaccharide donor 5 and acceptor 3 from one precursor and then to combine them to get
tetrasaccharide 6. Glucosylation of the trisaccharide acceptor 9 with tetrasaccharide donor 8
proceeded smoothly to give heptasaccharide backbone. Stereoselectivity of each -glucosylation of
the whole scheme was controlled by -stereodirecting benzoyl group at O-6. [4] While high yields
of all glucosylations were attained due to the choice of N-phenyl-trifluoracetidoyl leaving group and
MeOTf as a promoter. [5] Free heptasaccharide 1 was converted to BSA and biotin conjugates
using amino group of the spacer.
1. A. Gastebois; C. Clavaud; V. Aimanianda; J. P. Latgé Future Microbiology 2009, 4, 583.
2. D. Maubon; S. Park; M. Tanguy; M. Huerre; C. Schmitt; M. C. Prévost; D. S. Perlin; J. P. Latgé; A.
Beauvais Fungal Genetics and Biology 2006, 43, 366.
3. A. Beauvais; C. Schmidt; S. Guadagnini; P. Roux; E. Perret; C. Henry; S. Paris; A. Mallet; M. C. Prévost;
J. P. Latgé Cellular Microbiology 2007, 9, 1588.
4. B. S. Komarova; M. V. Orekhova; Y. E. Tsvetkov; N. E. Nifantiev Carbohydrate Research 2014, 384,
70.
5. B. S. Komarova; Y. E. Tsvetkov; Y. A. Knirel; U. Zähringer; G. B. Pier; N. E. Nifantiev Tetrahedron
Letters 2006, 47, 3583.
181
P71
SUPRAMOLECULAR STRUCTURES IN ADDUCTS OF
CYMANTRENECARBOXYLIC ACID WITH FIVE- AND SIX-MEMBERED
AROMATIC N-BASES
P.S. Koroteev, A.B. Ilyukhin, Zh.V. Dobrokhotova, V.M. Novotortsev
N. S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences
One of the goals of supramolecular chemistry is the search for new molecules that are potentially
capable of self-assembly owing to nonvalent interactions. The molecule of
cyclopentadienyltricarbonylmanganese (η5-C5H5)Mn(CO)3 (cymantrene), which has the “piano
stool” shape, besides of many other peculiarities, has specific properties as a potential building
block for supramolecular architectures both due to its special geometry and the nature of its
constituent moieties. Earlier we have studied the crystal-chemical behavior of anions of
cymantrenecarboxylic acid (η5-C5H4COOH)Mn(CO)3 (HL) and more sterically hindered βcymantrenoylpropionic acid (η5-C5H4CO(CH2)2COOH)Mn(CO)3 combined with alkaline metals
cations and with protonated molecules of polytopic nitrogen bases, which have various geometries
and provide opportunities for supramolecular interactions [1].
New derivatives of HL and polytopic aromatic N-bases: imidazole (I), pyrazole (II), 3-amino-1,2,4triazole (III), 4-amino-1,2,4-triazole (IV), 2-aminopyridine (V), 3-aminopyridine (VI), 4aminopyridine (VII), 2,4-diamino-6-hydroxypyrymidine (VIII) were obtained and characterized by
X-ray diffraction.
It has been shown that two- and three-dimensional supramolecular structures of these derivatives
are formed owing to special properties of the cymantrene moiety, in particular its ability to form
CO…H hydrogen bonds (HBs), but the type of the structure is mostly determined by the geometry of
the cation and by its capability of HBs formation (Fig.1). The possibility of organic molecules of
various nature to self-organize due to protonation and/or HBs formation and with regard to specific
geometries is discussed.
Fig 1. Fragments of the structures of VII·HL (left) and VIII·HL (right).
[1] A.B. Ilyukhin, P.S. Koroteev, M.A. Kiskin, Zh.V. Dobrokhotova, V.M. Novotortsev, Journal of
Molecular Structure, 1033 (2013) 187–199
Acknowledgements: This study was financially supported by the RFBR (No. 13-03-12428, 14-03-00463), the
Council on Grants of the President of the RF (NSh-1712.2014.3) and the Presidium of the Russian
Academy of Sciences.
182
P72
NUCLEOFILIC BROMO- AND IODODIFLUOROMETHYLATION OF
ALDEHYDES
M.D. Kosobokov, V.V. Levin, M.I. Struchkova, A.D. Dilman
IOC RAS, Moscow, Russia
Nowadays, Ruppert−Prakash reagent (Me3SiCF3)1 and its functionalized analogues2, 3 are widely
applicable fluorinated reagents in organic synthesis. Indeed, these air stable silanes are convenient
agents for nucleophilic fluoroalkylation reactions. They exhibit their nucleophilic reactivity under
silaphilic Lewis base activation, generating a pentacoordinate intermediate, which could react with
a suitable electrophile (e.g., aldehydes). Reactions of the Ruppert−Prakash reagent (X =F) and
chloro-substituted analog (X = Cl), as well as many other functionalized silanes, follow this
pathway.
However, reactions of a bromo-substituted silane (X = Br) with aldehydes mediated by a fluoride
ion have been unsuccessful, presumably owing to facile decomposition of anionic intermediate to
difluorocarbene. Indeed, silane Me3SiCF2Br can generate difluorocarbene even in the presence of
weak Lewis bases such as chloride and bromide ions. While (bromodifluoromethyl)trimethylsilane
(1a) can be readily obtained from the Ruppert−Prakash reagent, iodinated silane (1b) has not been
known. We prepared silane 1b from silane 1a in 70% yield by the bromine/zinc exchange followed
by iodination.
Then, we developed a method for nucleophilic bromo- and iododifluoromethylation of aldehydes
using bromo- and iodo-substituted difluoromethyl silicon reagents (Me3SiCF2X). The reaction is
performed in the presence of a combination of tetrabutylammonium and lithium salts Bu4NX/LiX
(X = Br or I) in propionitrile.4
It is believed that, in this process, a short-lived halodifluoromethyl carbanion serves as nucleophile,
which is reversibly generated from difluorocarbene and a halide anion.
This work was supported by the Russian Science Foundation (project 14-13-00034).
[1] Liu, X.; Xu, C.; Wang, M.; Liu, Q. Chem. Rev. 2014. ASAP, doi:10.1021/cr400473a
[2] Kosobokov, M. D.; Dilman, A. D.; Struchkova, M. I.; Belyakov, P. A.; Hu, J. J. Org. Chem.
2012, 77, 2080−2086.
[3] Kosobokov, M. D.; Dilman, A. D.; Levin, V. V.; Struchkova, M. I. J. Org. Chem. 2012, 77,
5850−5855.
[4] Kosobokov M. D., Levin V. V., Struchkova M. I., Dilman A. D. Org. Lett. 2014, 16, 3784.
183
P73
NEW REGIOSELECTIVE ROUTE TO 5-CARBOXY-1,2,3-TRIAZOLES VIA
PALLADIUM-CATALYZED CARBONYLATION OF 5-IODO-1,2,3TRIAZOLES
Y.N. Kotovshchikov, G.V. Latyshev, N.V. Lukashev, I.P. Beletskaya
Chemistry Department, Lomonosov Moscow State University, Moscow, Russia
Various compounds containing 1,2,3-triazole moiety are of great importance in coordination and
supramolecular chemistry, medicine, polymer and materials sciences [1]. In particular, some 5carboxy-1,2,3-triazoles were shown to be kinases inhibitors as well as to exhibit antiviral and
antibacterial effects [2]. So far, the only synthetic route to these compounds was thermal [3+2]cycloaddition of organic azides to propiolic acid derivatives. The main drawback of the method is
low regioselectivity. Formation of two regoisomers diminishes yields of desired 5-carboxy-1,2,3triazoles and complicates isolation of the products. Since 5-iodo-1,2,3-triazoles can be prepared
from 1-iodoalkynes and azides under Cu(I) catalysis [3], the subsequent carbonylation reaction
could became a new regioselective approach to 5-carboxy-1,2,3-triazoles.
We have shown that alkoxycarbonylation of 5-iodo-1,2,3-triazoles could be performed under mild
reaction conditions with 1 atm of CO in the presence of 5 % Pd(OAc)2. Various functional groups
(ester, hydroxyl, ketone, nitro) were tolerated and a number of 5-methoxycarbonyl-1,2,3-triazoles
were obtained in good to excellent yields. The transformation appeared sensitive to steric effects,
and bulky substituents led to decrease in reaction rate and/or yield.
This work was supported by RFBR (grant № 11-03-00265-а).
1. (a) M. Meldal, C. W. Tornøe. Chem. Rev. 2008, 108, 2952; (b) J. E. Hein, V. V. Fokin. Chem. Soc. Rev.
2010, 39, 1302.
2. (a) H. Cheng, J. Wan, M.-I. Lin, Y. Liu, X. Lu, J. Liu, Y. Xu, J. Chen, Z. Tu, Y.-S. E. Cheng, K. Ding. J.
Med. Chem. 2012, 55, 2144; (b) G. S. Gadaginamath, M. G. Bhovi. Indian J. Chem., Sect. B: Org. Chem.
Incl. Med. Chem. 2005, 44, 1068.
3. J. E. Hein, J. C. Tripp, L. B. Krasnova, K. B. Sharpless, V. V. Fokin. Angew. Chem., Int. Ed. 2009, 48,
8018.
184
P74
A GENERAL APPROACH TO THE SYNTHESIS OF THIOPHENECONTAINING ELECTRON-DONOR AND -ACCEPTOR FRAGMENTS FOR
CONJUGATED POLYMERS FOR SOLAR PHOTOVOLTAIC CELLS
I.O. Konstantinov1, M.M. Krayushkin1, M.L. Keshtov2, S.A. Kuklin2, V.S. Kochurov3, N.A.
Radychev4, A.R. Khokhlov2
1 - N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
2 - A.N. Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia
3 - M.V. Lomonosov Moscow State University, Physical Department, Moscow, Russia
4 - Carl von Ossietzky University of Oldenburg, Physical Department, Oldenburg, Germany
The goal of this work was developing a general method for creating both electron-donor, and
electron-acceptor moieties in terms of dithienylethenes to use them for preparation of new
conjugated polymers as an electroactive material for solar cells. Bis(trimethylstannyl)-2-dodecylbenzotrithiophene monomer (1) as a donor in D–A copolymers was synthesized for the first time
from the corresponding dithienylethene with thiophene bridge [1].
C 17 H 35
S
N
H 31C 15
N
S
Br
S
S
S
1
S
C 8H 17
N
N
1
S
Br
2
S
Sn
R
N
R
C 12 H 25
Br
Sn
S
S
Br
Br
S
S
Br
Br
S
S
Br
4
C 12 H 25
3 .R =
O
Et
C10 H23
5 .R 1 =
S
S
C8 H17
Bu
S
*
S
6 .R 1 =
Ar
P
n*
O
C10 H23
C8 H17
Dibromides 2-6 were synthesized also analogously from dihetarylethenes [1,2] and used as
monomers of the electron-acceptor nature.
New narrow-band conjugated polymers of type P with a rigid alternation of donor and acceptor
units were prepared on the basis of these monomers, under the Stille reaction conditions in the
presence of tetrakis(triphenylphosphine)palladium as a catalyst [3,4].
The thermal, optical, electrochemical, and photovoltaic properties of the copolymers were studied
[5].
1. M.M. Krayushkin and M.A. Kalik, Syntheses of Photochromic Dihetarylethenes. In: Katritzky,
editors: Advances in Heterocyclic Chemistry, Vol. 103, Oxford: Academic Press; 2011, p. 1-59.
2. Shirinian, V.Z., Lonshakov, D.V., Kachala, V.V., Zavarzin, I.V., Shimkin, A.A., Lvov, A.G.,
and Krayushkin, M.M., J. Org. Chem., 2012, vol. 77, p. 8112.
3. Keshtov, M.L., Marochkin, D.V., Kochurov, V.S., Komarov, P.V., Parashchuk, D.Yu.,
Trukhanov, V.A., and Khokhlov, A.R., Vysokomol. Soedin., Ser. B., 2014, vol. 56, no. 1, p. 1.
4. Keshtov, M.L., Toppare, L., Marochkin, D.V., Kochurov, V.S., Parashchuk, D.Yu., Trukhanov,
V.A., and Khokhlov, A.R., Vysokomol. Soedin., Ser. B., 2013, vol. 55, no. 6, p. 723.
5. M.L. Keshtov, S.A. Kuklin, V.S. Kochurov, I.O. Konstantinov, M.M. Krayushkin, N.A.
Radychev, and A.R. Khokhlov, Doklady Chemistry, 2014, Vol. 454, Part 2, pp. 25–31.
185
P75
PHOTOCHEMICAL REARRANGEMENT OF CHROMONES AND
BENZOFURANS
K.S. Chudov1, K.S. Levchenko1, V.N. Yarovenko1, M.M. Krayushkin1, O.I. Kobeleva2, T.M.
Valova2, V.A. Barachevsky2, E.P. Grebennikov1
1 - N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
2 - Photochemistry Center, Russian Academy of Sciences, Moscow, Russia
At present optical information recording in the existing ODs is based on thermoinduced
transformation processes of substances that change the reflection properties under the action of
light. Prospects for increasing the information capacity of ODs are related to the development of
multilayered photosensitive detection media based on organic compounds that being irradiated
undergo irreversible photochemical transformations of the initial non-fluorescing compounds into
fluorescent photoproducts. It has recently been shown that UV-irradiated acylchromones I that do
not manifest fluorescence are irreversible rearranged to fluorescent furano[3,4-b]chromenones II.
Based on the latter, we are developing multilayered detection media for ODs of the WORM archive
type [1,2].
O
R
O
R
O
2
O
O
UV
R
R
2
O
1
O
I
1
R
II
R
2
R , R , R = H , F G , A r, H e ta r
1
O
We synthesized a set of benzofurans IV with a highlighted furylpropenonic fragment and
demonstrated that they under UV-illumination also transformed into tricondensed derivatives V,
that is the photorearrangement by all appearances has a common character. It is worthy noted that
initial compounds IV did not possess fluorescence whereas the products V did.
H
R
2
R
O
O
O
O
R
O
B rC H 2C O R 2
1
2
O
UV
O
III
R 1= M e , B r
O
R
R
1
IV
1
R = M e , B r; R
2
1
V
O
= Ph, Ar
The fluorescence properties of the compounds due to irreversible photochemical transformations of
chromones and benzofurans in toluene were studied. The quantum yields of the photoproducts were
measured. Some relationships between the fluorescence properties of the photoproducts and their
structure were revealed.
A part of the compounds are characterized by a high Stokes shift and other profitable properties that
provide their practical application in photosensitive detection media with nondestructive
fluorescence reading optical information.
1. V.A. Barachevsky, O.I. Kobeleva, T.M. Valova, A.O. Ait, A.A. Dunaev, A.M. Gorelik, M.M.
Krayushkin, K.S. Levchenko, V.N. Yarovenko, V.V. Kyiko, E.P. Grebennikov, Opt. Mem. &
Neur. Networks; 19 (2010), 187.
2. V.A. Barachevsky, M.M. Krayushkin, V.V. Kyiko, E.P. Grebennikov, Phys. Status Solidi C, 8
(2011), 2841.
186
P76
NEW CHROMONE-CONTAINING LIGANDS
K.A. Myannik1, V.N. Yarovenko1, K.S. Levchenko2, M.M. Krayushkin1
1 - N.D. Zelinsky Institute of Organic Chemistry, RAS, Moscow, Russia
2 - Central Research Technological Institute “Tekhnomash", Moscow, Russia
Chromone derivatives are of doubtless interest as bioactive compounds and elements of detecting
media for multilayer optical discs of superhigh capacity. We showed the possibility to synthesize
chromone-containing ligands containing fragments of thiohydrazides of oxaminic acids 1-9.
F
S
HN
HN
O
N
HN
S
S
NH
O
S
O
O
N
O
F
F
O
NH
COOEt
NH
N
F
O
O
1
2
3
O
F
S
HN
HN
HN
S
S
O
NH
O
N
O
NH2
4
S
O
NH
O
N
O
NH2
O
COOEt
NH
O
N
O
NH2
6
5
F
S
HN
HN
S
S
O
HO
O
7
N
O
O
NH
O
O
HO
8
N
HN
S
NH
HO
9
187
O
NH
O
N
O
NH2
COOEt
P77
NEW COMPLEX STRUCTURES BASED ON OXAMINIC ACID
THIOHYDRAZIDES
M.M. Krayushkin, V.N. Yarovenko, I.V. Zavarzin
N.D. Zelinsky Institute of Organic Chemistry, RAS, Moscow, Russia
It is known that among thiohydrazides there are many drugs of different action, which is enhanced,
in many cases, in the presence of metal cations. We showed a possibility to synthesize complexes
from the ligands containing fragments of oxaminic acid thiohydrazides 1-3.
1
2
3
The geometric parameters of synthesized complex 1 were studied by X-ray diffraction analysis (Fig.
1).
Fig. 1
Fig. 2
The square-planar coordination mode of nickel is attained due to two additional atoms: S i with a
distance of 3.407(2) Å and Oii with a distance of 3.451(4) Å (symmetry transform i: x, y+1, z and i:
x, y-1, z ) with the formation of a distorted octahedron around the nickel atom. An infinite chain is
thus formed (Fig. 2).
188
P78
THREE-COMPONENT CONDENSATION OF IMINOAZOLIDINONES
WITH ALDEHYDES AND MELDRUM`S ACID. SYNTHESIS AND STUDY
OF PROPERTIES OF THE IMIDAZOPYRIDINE-2,5-DIONES
K.S. Krylov, A.N. Komogorttsev, B.V. Lichitsky, A.A. Dudinov, M.M. Krayushkin
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Multicomponent reactions are indispensable tools which are used for the construction of different
heterocyclic systems. The marked advantage of such a reactions are the versatility and efficiency of
synthesis of the new organic materials. The diversity of the multicomponent reactions allows to
create a broad set of compounds without using the methodology of the complicated multistage
synthesis. The present work devoted to the development of our previously elaborated method, based
on multicomponent reaction of the heterocyclic enamines, carbonyl compounds and the Meldrum`s
acid. We have proposed the versatile method of preparation of the previously unknown 7-aryl-1phenyl-1,6,7,7-tetrahydro-4H-imidazo[4,5-b]pyridine-2,5-diones 1 based on the three component
condensation of iminoazolidines 2, aldehydes 3 and the Meldrum`s acid 4.
HN
H
N
N
O
O
+
ArC HO
+
N
O
O
H
N
O
N
O
O
O
Et O H
N
Ph
Ph
Ar
2
3
1
4
The properties of the obtained imidazopyridine-2,5-diones 1 were investigated. It is demonstrated
that compounds of type 1 undergo the acid hydrolysis with formation of previously unknown 5substituted 1-phenylimidazolidine-2,4-diones 5.
O
O
H
N
H
N
N
H2 N
O
N
AcO H
N
O
Ph
Ar
1
Ar
O
Ph
5
References
1. B. V. Lichitsky, R. M. Belyi, A. N. Komogortsev, A. A. Dudinov, M. M. Krayushkin, Russ.
Chem. Bull., Int. Ed., 2013, 62, 1026-1031.
189
P79
RADICAL CROSS-DEHYDROGENATIVE C-O COUPLING OF 1,3DICARBONYL COMPOUNDS WITH HYDROXYLAMINE DERIVATIVES
I.B. Krylov, A.O. Terent`ev, B.N. Shelimov, G.I. Nikishin
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russian
Federation
Cross-dehydrogenative coupling, as a rule, is a reaction, in which two different starting molecules
are connected by a new bond with the elimination of one hydrogen atom from each of the
molecules. In the last decade, these reactions have attracted great attention because they can be used
to form a new bond with almost the maximum possible atom economy and do not require additional
synthetic steps for the introduction of functional groups (Hal, OTf, BR2, SiR3, SnR3, ZnHal, etc.)
that are necessary in other approaches to the cross-coupling.
The cross-dehydrogenative С-С coupling was studied in most detail; the C-N, C-P and C-O crosscoupling reactions are less well developed. It is difficult to achieve high selectivity in the oxidative
C-O coupling because the starting compounds are prone to side oxidation and fragmentation
reactions giving, for example, alcohols and carbonyl compounds.
In the present work, the cross-dehydrogenative С–O coupling of β-dicarbonyl compounds with
oximes,[1] N-hydroxyimides[2] and N-hydroxyamides[2] was performed for the first time.
The reaction proceeds in the presence of the different metal-containing oxidants: KMnO4,
Mn(OAc)2/KMnO4, Co(OAc)2/KMnO4, Mn(OAc)3•2H2O, MnO2, Mn(acac)3, Fe(ClO4)3,
Cu(ClO4)2•6H2O, Cu(NO3)2•2.5H2O, and (NH4)2Ce(NO3)6; yields are 27–94%. The synthesis can
be easily scaled up to gram quantities of the target products. The method is applicable for a wide
variety of β-diketones and β-keto esters; 2-substituted malonic esters and heteroanalogues of
β-dicarbonyl compounds, 2-substituted malononitriles and cyanoacetic esters, are substantially less
reactive in the cross-dehydrogenative coupling with tested hydroxylamine derivatives.
Apparently, the oxidant serves two functions in the cross-dehydrogenative coupling reaction: the
generation of N-oxyl radicals from hydroxylamine derivatives and the one-electron oxidation of
β-dicarbonyl compounds. The formation of N-oxyl radicals was confirmed by ESR spectroscopy.
Acknowledgements. This work was supported by the Russian foundation for Basic Research (Grant
13-03-12074).
1. I. B. Krylov, A. O. Terent’ev, V. P. Timofeev, B. N. Shelimov, R. A. Novikov, V. M.
Merkulova, G. I. Nikishin, Iminoxyl Radical-Based Strategy for Intermolecular C-O Bond
Formation: Cross-Dehydrogenative Coupling of 1,3-Dicarbonyl Compounds with Oximes // Adv.
Synth. Catal., 2014, 356, 2266–2280. DOI: 10.1002/adsc.201400143
2. A. O. Terent’ev, I. B. Krylov, V. P. Timofeev, Z. A. Starikova, V. M. Merkulova, A. I.
Ilovaisky, G. I. Nikishin, Oxidative C-O Cross-Coupling of 1,3-Dicarbonyl Compounds and
Their Heteroanalogues with N-Substituted Hydroxamic Acids and N-Hydroxyimides // Adv.
Synth. Catal. 2013, 355, 2375–2390. DOI: 10.1002/adsc.201300341
190
P80
THE FIRST ENANTIOSELECTIVE ORGANOCATALYTIC REACTION IN
SUPERCRITICAL CARBON DIOXIDE: ASYMMETRIC MICHAEL
ADDITION OF DIPHENYLPHOSPHITE TO α-NITROALKENES
E.V. Kryuchkova, I.V. Kuchurov, A.G. Nigmatov, A.S. Kucherenko, S.G. Zlotin
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospekt, 47,
119991 Moscow, Russia
Recently, we discovered [1] that asymmetric organocatalytic reactions can be efficiently carried out
in liquid carbon dioxide. We have expected that the use of CO2 in the supercritical state (sc-CO2) as
a reaction medium may be even more promising as it is characterized by higher diffusion rates and
a unique capability of dispersing poorly soluble reagents, thus enhancing the reaction scope, rates
and selectivity.
Herein we report that α-nitroalkenes 2 enantioselectively accept diphenylphosphite (1) in sc-CO2 in
the presence of bifunctional tertiary amines 4 and 5 (5 mol %)) bearing the squaramide fragment to
afford corresponding β-nitrophosphonates 3 in high yields and with enantiomeric access of up to
94% ee [2]. In this way enantiomeric β-nitrophosphonates 3 and ent-3, which are precursors of
optical antipodes of β-amino phosphonic acid derivatives that occur in nature and possess valuable
biological activities, were synthesized. Furthermore, we disclosed a significant potential of sc-CO2
for the fractional extraction of products and recovery of precious chiral catalyst. The obtained
results contribute to green chemistry as they eliminate toxic organic solvents originated from
exhausting hydrocarbon resources and facilitate separation and purification steps that usually have
the highest environmental impact in chemical processes.
References
1. A.G. Nigmatov, I.V. Kuchurov, D.E. Siyutkin, S.G. Zlotin, Tetrahedron Lett. 2012, 53, 3502.
2. I.V. Kuchurov, A.G. Nigmatov, E.V. Kryuchkova, A.A. Kostenko, A.S. Kucherenko, S.G.
Zlotin, Green Chem. 2014, 16, 1521.
191
P81
SYNTHESIS OF NEW CLASS OF ORGANIC PEROXIDES:
IODOPEROXIACETALS, BY TREATMENT OF ENOLE ETHERS WITH
IODINE-HYDROPEROXIDE SYSTEM
A.N. Kulakova, A.T. Zdvizhkov, A.O. Terentev, R.A. Novikov, G.I. Nikishin
N. D. Zelinsky institute of organic chemistry, Laboratory for Studies of Homolytic Reactions,
Moscow, Russia
Organic peroxides are very common for development of antitumor and antiparasitic drugs.
However, effectiveness of drugs reduces due to the mobilization of cells defense mechanisms with
respect to specific substances. This problem is solved by the development of new classes of
biological compounds, as well as their chemical modifications.
In the present work, we studied the interaction of mono-and bicyclic enol ethers with a system of I2,
hydroperoxide. This system allows getting number of new peroxide compounds containing an
iodine atom, which makes possible further modification of the peroxide molecule.
Commercially available monocyclic enole esters of 2,3-dihydrofuran and 3,4-dihydro-2H-pyran
were selected as starting materials, as well as their bicyclic analogs that can be synthesized by a
known method.
Firstly, we studied the interaction of monocyclic enol ethers with the system, I2-ButOOH (TBHP)
and I2-tetrahydropyranyl hydroperoxide (THPHP). We have proposed a method to obtain
iodoperoxide with yields up to 90%. The reaction is carried out in diethyl ether at 0 ° C in the
presence of 4-fold excess hydroperoxide and an equivalent amount of iodine.
Having developed iodoperoxidation method, we investigated the reaction of the bicyclic enole
ethers with the I2-H2O2 system. Iodoperoxides were obtained with yield of 80%. The reaction was
carried under the action of iodperoxidation monocyclic enole ethers at - 40 ° C. When using a more
bulky t-BuOOH were obtained addition products the peroxide to double bond not containing iodine
atom. In the case of THPHP reaction did not proceed at all.
In this work the methodology of synthesis of a new class of organic peroxides - vicinal
iodperoxyacetals and ketals based on mono-and bicyclic enole ethers was developed. These
compounds may be useful for inventing new anticancer and antiparasitic drugs.
Acknowledgements
This work was supported by the Russian Science Foundation (Grant № 14-23-00150).
192
P82
APPLICATION OF AZA-COPE-MANNICH REACTION FOR HIGHLY
EFFICIENT STEROSELECTIVE SYNTHESIS OF DERIVATIVES OF (2SR,
3ASR, 8ASR)-3A-METHYLOCTAHYDROCYCLOHEPTA[B]PYRROL4(1H)-ONE
I.N. Myasnyanko, E.R. Lukyanenko, A.V. Kurkin
M.V. Lomonosov Moscow State University
Saturated heterocyclic compounds are much more attractive objects for the development of new
drugs compared to traditionally used in medicinal chemistry heteroaromatic compounds, since they,
as a rule, possess better solubility, pharmacokinetic properties and bioavalability [1, 2]. In this
regard, development of efficient stereoselctive methods for the syntheis of such compounds (having
patent purity) is an important task for scientists working in drug discovery field.
Earlier, we developed highly efficient steroselective synthesis of cis- and trans-fused 3-substituted
octahydrocyclohepta[b]pyrrol-4(1H)-ones using aza-Cope-Mannich reaction as a key step [3, 4]. In
the presnt work we present simple highly efficient steroselective synthesis of 2-substituted cis-fused
octahydrocyclohepta[b]pyrrol-4(1H)-ones starting from cheap cyclohexene oxide using tandem of
aza-Cope and Mannich reactions as a key step.
Amino ketones 1 were obtained as sole stereoisomers in high overall yield, their structures were
confirmed by X-ray (for R = Ph and i-Pr).
This work was supported by Russian Foundation for Basic Research (projects 14-03-31685, 14-0331709, 14-03-01114).
1. Ritchie, T. J., Macdonald S. J. F., Young, R. J., Pickett S. D. Drug Discov. Today 2011, 16, 164171.
2. Meanwell, N. A. Chem. Res. Toxicol. 2011, 24, 1420-1456.
3. Belov, D. S., Lukyanenko, E. R., Kurkin, A. V., Yurovskaya, M . A. Tetrahedron 2011, 67,
9214-9218.
4. Belov, D. S., Lukyanenko, E. R., Kurkin, A. V., Yurovskaya, M . A. J. Org. Chem. 2012, 77,
10125-10134.
193
P83
SYNTHESIS AND TRANSFORMATIONS DERIVATIVES OF AMINO ACID
CONTAINING NITROGENOUS HETEROCYCLE
D.R. Latypova1, V.A. Dokichev1, Yu.V. Vahitova2
1 - Institute of Organic Chemistry Ufa SC RAS
2 - Institute of Biochemistry and Genetics Ufa SC RAS
The achievements of modern pharmacology and clinical medicine are largely determined by the
synthesis of new groups of physiologically active compounds. Compounds containing amino acid,
pyrrolidone and hexahydropyrimidine moieties are natural and important group of biologically
active compounds. A lot of them have a variety of pharmacological effects (anti-tumor, antiplatelet, anti-bacterial and anti-arrhythmic, etc.).
In order to develop effective regio- and stereoselective methods of synthesis of the biologically
active amino acids derivatives containing nitrogen heterocycle studied the interaction of CH-acids
(acetone, benzyl acetone, ethyl acetoacetate and 1,3-acetonedicarboxylic acid diethyl ester) with
formaldehyde, primary amines and amino acids in the Mannich reaction conditions. On the basis of
the synthesized 1,3-hexahydropyrimidines containing in the 5-position the acetyl and the ester
group 5-methyl-2,4-dihydro-3H-pyrazol-3-ones with amino acid moieties are obtained. It has been
established that the splitting of 1,3- hexahydropyrimidine cycle with hydrazine hydrate which
follow with retention of configuration of the optically active centers.
3-Diazopyrrolidin-2-ones that are of interest as structural fragments for production analogies of γaminobutyric acid - the chief inhibitory neurotransmitter in the mammalian central nervous system
are synthesized. A method of obtaining inaccessible heterocyclic compounds containing a
pyrazolo[1,5-c]pyrimidine moiety based on the van Alphen-Huettel rearrangement of products of
1,3-dipolar cycloaddition ─ 3-diazo-4-phenylpyrrolidone with dimethyl acetylenedicarboxylate and
5-diazo-exo-3-azatricyclo[5.2.1.02,6]decan-4-one with quinone is proposed.
Among the investigated groups of substances novel compounds that have cytotoxic properties
against both cell HEK293 and SH-SY-5Y are discovered.
194
P84
METAL/POLYMER NANOCATALYSTS FOR HYDROGEN-OXYGEN
MICRO-POWER ENERGY SOURCES
M.V. Lebedeva1, N.A. Yashtulov2, N.E. Minina1, K.S. Smirnov2, S.S. Gavrin2
1 - Lomonosov Moscow state university of fine chemical technologies, Moscow, Russia
2 - National research university "Moscow power engineering institute", Moscow, Russia
Development of highly active and stable nanoelectrocatalysts for micro-power energy sources
(MPES) on the basis of fuels conversion is one of the fundamental problems of modern science and
energy. The modification of solid polymer membranes (SPM) by metal nanoparticles of not only
the surface but also the volume is used to create efficient catalytically active, stable and cheap
materials for energy sources of new generation. The introduction of inorganic components makes it
possible to enhance the exploitation characteristics of the solid polymer membranes [1-3].
At present time the most relevant and promising energy sources are fuel cells with solid polymer
electrolyte (SPE) due to their extensive use in stationary applications and mobile electronic
equipment. Electrolyte in such system is proton exchange perfluorinated polymer with ionogenic
sulfo groups (–SO3H) of the Nafion® type (Du Pont) that provides unipolar conductivity on
hydrogen ions [1,2].
As nanostructured matrix-substrate in our work it was used the Nafion type solid polymer
membrane (SPM) with a thickness of less than 0.2 mm. The modification by one-component and
bimetallic nanoparticles of platinum and base metal of the SPM surface and volume promotes
additional catalytic oxidation of hydrogen-containing fuels (H2, C2H5OH, HCOOH, CH3OH and
others). Due to introduction of nano-sized metal in the polymer matrix and application of bimetallic
systems there is an increasing of the catalytic and functional activity of metal-polymer
nanocomposites and reduced the consumption of expensive Pt and Pd catalysts [1,2].
The aim of the present study was to establish the influence of the metal/polymers Pt/Nf and Pd/Nf
synthesis parameters on the catalytic activity of platinum nanoparticles in the hydrogen oxidation
and oxygen reduction reactions.
The platinum metal nanoparticles solutions were prepared by the radiation chemical reduction 60Co
in reverse micelle solutions [1,2]. By varying the synthesis conditions one can control the
nanoparticles size, content and functional properties. By means of the modern physico-chemical
research methods, as electron microscopy, x-ray phase analysis, cyclic voltammetry it was
performed the investigation of nanoparticle and nanocomposite functional properties. It was found
that when reducing the size of metal nanoparticles (less than 8 nm) catalytic activity of
metal/polymer nanocomposites (current density, catalytically active surface area) increases [1,2].
The work was supported by RFBR (grant 13-08-12407 ofi_m2).
References
[1] Yashtulov N.A., Flid V.R. Russ. Chem. Bull. 2013. V. 62. № 6. Р. 1332-1337.
[2] Yashtulov N.A., Revina A.A., Lebedeva M.V., Flid V.R. Kinetics and catalysis. 2013. V. 54. №
3. P. 336-339.
[3] Limpattayanate S., Hunsom M. Renewable Energy. 2014. V. 63. № 5. P. 205-211.
195
P85
TRÖGER BASE AS A SINGLE SOURCE OF CHIRALITY IN A NEW
BIS(SALICYLALDIMINATO) CATALYST FOR RING-OPENING OF
PROPYLENE OXIDE
D.A. Lenev1, R.G. Kalinin1, V.A. Kardash1, A.V. Kiselyova1, I.O. Konstantinov2
1 - NIOST LLC, Tomsk, Kuzovlevskii trakt 2, str.270
2 - Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47,
Moscow
Recently many privileged catalysts, variations of C2-symmetric Schiff base salen ligands of
Jacobsen and Katsuki, modified by pendant ammonium arms with nucleophilic counterions, and
corresponding cobalt catalysts have been developed.[1][2][3] They have been intensively used in
the popular field of stereoregular co-polymerization of alkene oxides with carbon dioxide to yield
regular polymers – polyalkene carbonates, such as polypropylene carbonate PPC or
polycyclohexene carbonate PCHC. Stereotacticity and stereointegrity of PCHC influences its
crystallinity, melting point and thermal stability, which is higher in the case of stereocomplex –
polymeric racemate.[1] Co-polymerization of (rac)-propylene oxide with CO2 yields stereogradient
racemic stereocomplex PPC with improved thermal stability, and thus, processability.[2] The PPC
material has been commercialized and the molecular formulas of the respective catalysts have been
patented heavily.[3]
Tröger base (TB)[4] could represent valuable asset for its practical use in asymmetric catalysis. In
order to rely upon TB not only as fascinating, but also as privileged structure, we followed an
algorithm in building a molecule with a single C2 axis for the single TB diamine and single salen
core, aligning sequentially the carbon of NCN bridge, the metal ion, and the center of (N)CC(N)
bond of unsubstituted 1,2-ethylenediamine.
In this preliminary report we present an approach to the synthesis of the newly designed salen
complex 1 with chirality solely due to asymmetric N atoms of enantiopure TB, and we report the
preparation of the system capable of efficient catalysis of cycloaddition of propylene oxide with
CO2 to yield cyclic propylene carbonate with high TON and TOF.
1
1. X.-B. Lu, W.-M. Ren, G.-P. Wu, Acc. Chem. Res., 2012, 45, 1721-1735; G.-P. Wu, W.-M. Ren, Y. Luo,
B. Li, W.-Z. Zhang, X.-B. Lu, J. Am. Chem. Soc. 2012, 134, 5682-5688
2. K. Nakano, S. Hashimoto, M. Nakamura, T. Kamada, K. Nozaki, Angew. Chem. Int. Ed. 2011, 48684871; B. Y. Lee, A. Cyriac, Nature Chem., 2011, 3, 505-507
3. A. Tullo, Capturing Carbon, in: Chem. Eng. News, June 23, 2008, vol. 86(25), p.21; Novomer, Inc.: WO
2011/163133 2011 (S. D. Allen, A. E. Cherian, C. A. Simoneau, J. J. Farmer)
4. F. Vögtle, Fascinating molecules in Organic Chemistry, Wiley, Chichester, UK, 1992; B. Dolenský, M.
Havlík, V.Král, Chem. Soc. Rev. 2012, 41, 3839-3858
196
P86
GEMINAL SILICON/ZINC REAGENT AS AN EQUIVALENT OF
DIFLUOROMETHYLENE BIS-ANION
V.V. Levin, A.A. Zemtsov, M.D. Kosobokov, A.D. Dilman
IOC RAS, lab.8, Moscow, Russia
Elaboration of new methods for the synthesis of fluoroorganic compounds is important owing to
unique effect of fluorine atoms on their biological activity. Synthetic methods based on the
introduction of fluorinated fragments into organic substrate are most widely presented. While
various methods for the introduction of the CF3-group have been documented, approaches for the
synthesis of compounds bearing CF2-fragment notably less abundant. At the same time this
fragment is isosteric to ethereal oxygen, which makes compounds with this moiety highly attractive
as promising pharmaceuticals.
Typically, Synthesis of CF2-containing products involves
deoxofluorination reaction or relies on building block approach. Also we recently described a
strategy for assembling these compounds from difluorocarbene, nucleophile and electrophile1.
We present a germinal silicon/zinc binucleophilic reagent (1) for coupling with two electrophilic
spesies2. This reagent conveniently prepared by cobalt-catalyzed bromine/zinc exchange in
Me3SiCF2Br using isopropylzinc iodide.
Under the copper catalysis reagent 1 smoothly reacts with allylic halides with formation of
fluorinated silanes 2. This silanes were employed as nucleophilic reagents with a range of
aldehydes, provides after work-up the fluorinated alcohols 3. In this products both nucleophilic sites
of initial reagent 1 successively replaced by two electrophiles.
Acknowledgements. This work was supported by the Ministry of Sience (project MD4750.2013.3), Russian Foundation tor Basic Reseach (projects 13-03-12074, 14-03-00293, 14-0331253_mol_a, 14-03-31265_mol_a)
[1] Levin, V.V.; Zemtsov, A.A.; Struchkova, M. I.; Dilman, A.D. Org. Lett. 2013, 15, 917–919.
[2] Kosobokov, M. D.; Levin, V.V.; Zemtsov, A.A.; Struchkova, M. I.; Korlyukov, A. A.;
Arkhipov, D. E.; Dilman, A.D. Org. Lett. 2014, 16, 1438–1441.
197
P87
THERMAL AND ALUMINUM OXIDE INDUCED GAS-PHASE RINGOPENING TRANSFORMATION OF GEM-DIFLUORO- AND GEMFLUOROCHLOROCYCLOPROPANES WITH FORMATION OF 2FLUORO- OR 2-CHLOROBUTA-1,3-DIENES
N.V. Volchkov, M.B. Lipkind, M.A. Novikov, O.M. Nefedov
N.D. Zelinsky Institute of Organic chemistry of Russian Academy of Sciences, Leninsky prospect
47, 119991, Moscow,Russian Federation
It was found that gem-fluorochlorocyclopropanes 1a-d are converted into corresponding 2fluorobuta-1,3-dienes 3а-d under gas-phase pyrolysis in flow tube-reactor at 400-450°С as result of
thermal cyclopropyl-allylic ring opening transformation and dehydrochlorination. Under analogous
conditions gem-difluorocyclopropanes 2a-d undergo only thermal fragmentation with elimination
of difluorocarbene to give alkenes.
F
A l2 O 3
Cl
R
R
1 7 0 -2 5 0 ° C
R
Cl
R
1
R
flo w
2
R
1
R
flo w
CH3
1
2
2
1
R = R = H , R = C H 3 (a );
1
R
1 a -d
4 a -d (4 5 -6 5 % )
F
R
4 0 0 -4 5 0 ° C
2
2
3 a -d (3 5 -7 5 % )
1
2
R = R = H , R = C H 3 (b );
1
2
R = R = H , R = C H 3 (c ); R = R = H , R = C l (d );
R
R
F
2
4 0 0 -4 5 0 ° C
+
R
1
CH3
:C F 2
flo w
R
R
A l2 O 3
F
R
1
2
CH3
1 7 0 -2 5 0 ° C
flo w
2 a -d
The character of thermal transformation of 1a-d and 2a-d is changed if the pyrolysis carry out in the
presence of Al2O3. In this case gem-difluorocyclopropanes 2a-d can be converted into 2-fluorobuta1,3-dienes 3а-d at 170-250°С as result Al2O3 promoted breaking of very strength carbone-fluorine
bond that induce cyclopropyl-allylic transformation and dehydrofluorination. The ability of Al2O3
to activate the breaking С-F-bond cause also the promotion and the alteration of selectivity for ringopening transformation of gem-fluorochlorocyclopropanes 1a-d. In contraste to homogeneous
pyrolysis, heterogeneous thermolysis of 1a-d in the presence of Al2O3 at 170-250°С gave 2chlorobuta-1,3-dienes 4а-d.
198
P88
AN IMPROVEMENT OF THE CATALYTIC PERFORMANCE IN THE
ASYMMETRIC MICHAEL REACTION OF PRIMARY AMINE TAGGED
TO AN N-(CARBOXYALKYL)IMIDAZOLIUM CATION
V.G. Lisnyak, A.S. Kucherenko, S.G. Zlotin
IOC RAS, Laboratory 11, Moscow, Russia
A
(1S,2S)-1,2-diphenylethane-1,2-diamine
derivative
modified
with
an
N-(4–
carboxybutyl)imidazolium cation and PF6 anion has been developed and applied as a recyclable
organocatalyst of the asymmetric 1,4-conjugate addition of 4-hydroxy-2H-chromen-2-one to 1substituted buten-3-ones or cyclohexen-3-one to afford corresponding Michael adducts in high
yields (up to 97 %) and enantioselectivities (up to 90 % ee) [1]. The most active (S)-enantiomer of
the clinically useful anticoagulant warfarin was prepared in this way. The catalyst exhibited better
recyclability than its known analog [2], which does not contain a carboxy group: it could be recycled
5 times in the reaction without a significant decrease in product yield or ee values. Gradual
deactivation of the catalyst was caused by leaching during workup rather than by off-cycle reactions
between the catalyst and reagents.
The work was financially supported by the Russian Foundation of Basic Research (project 12-0300420).
[1] A. S. Kucherenko, V. G. Lisnyak, A. O. Chizhov, S. G. Zlotin, Eur. J. Org. Chem., 2014, 3808.
[2] A. S. Kucherenko, D. E. Siyutkin, A. G. Nigmatov, A. O. Chizhov, S. G. Zlotin, Adv. Synth.
Catal. 2012, 354, 3078.
199
P89
SYNTHESIS AND SPECTRAL FEATURES OF NOVEL PHOTOCHROMIC
DIARYLETHENES OF AZOLE SERIES
A.G. Lvov1, E.Yu. Bulich2, A.M. Yanina2, A.M. Kavun3, V.Z. Shirinian1, M.M. Krayushkin1
1 - N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
2 - D.I. Mendeleev University of Chemical Technology of Russia, Moscow, Russia
3 - Higher Chemical College, D.I. Mendeleev University of Chemical Technology of Russia,
Moscow, Russia
Diarylethenes with heterocyclic aromatic moieties are widely studied to develop different
electronics devices, such as optical memory and molecular switches [1]. To develop new
photochromic systems with improved spectral properties we have proposed a new type of the
photochromic diarylcycloalkenones of azole series. Various novel photochromic diarylethenes
bearing cyclopentenone or cyclohexenone rings as ethene bridge and azole residues (oxazole,
imidazole, pyrazole and thiazole derivatives) as aryl moieties have been synthesized. Ketoesters 1
are the key compounds in these syntheses which were prepared from commercially available
reagents in two stages. To introduce diverse functional groups in ethene bridge and aryl moieties
the various synthetic methods (C-alkylation, Nazarov, Michael and Knoevenagel reactions) have
been used.
O
Br
Ar
Ar
O
2
1
C O 2Et
O
2
1
Ar
1
Ar
2
1
A lk y la tio n + K n o e v e n a g e l c o n d e n s a tio n
O
O
1.
H
Ar
2
2.
H
Ar
3
O
Ar
3
A r 1 ,2 ,3 =
3
1
Ar
1
Ar
N
N
2
Me
Ar Me
O
K n o e v e n a g e l c o n d e n s a tio n + N a z a ro v c y c liz a tio n
Ph
O
Ar
2
O
4
1
Ar
1
Ar
Ar
S
Me
Ph
N
R
N
N
Me
N
Ph
Ph
2
M ic h a e l a d d itio n + K n o e v e n a g e l c o n d e n s a tio n (o n e -p o t)
Me
S
Me
The spectral characteristics of the obtained photochromic compounds as well as some features of
their preparation methods will be also discussed.
Acknowledgments:
This work was financial supported by Russian Foundation for Basic Research (Grant 14-03-31871).
References:
[1] M. Irie; Chem. Rev. 2000, 100, 1685.
200
P90
NEW PHOTOINDUCED REARRANGEMENT OF DIARYLETHENES
A.G. Lvov1, A.M. Kavun2, V.Z. Shirinian1, V.V. Kachala1, M.M. Krayushkin1
1 - N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
2 - Higher Chemical College, D.I. Mendeleev University of Chemical Technology of Russia,
Moscow, Russia
Diarylethenes (stilbenes) are one of the most reactive systems in photochemistry. Their cis/trans
isomerization, [2+2] cycloaddition and photocyclization reactions are widely known. Among them,
the photocyclization of diarylethenes is a subject of long standing interest. This process proceeds in
accordance with the Woodward-Hoffmann rule by conrotatory 6π-electrocyclization mechanism of
the cis-form of stilbenes I leading to the formation of the thermodynamically less stable isomer,
4a,4b-dihydrophenanthrene II, which is used in different transformations depending upon the
structure nature and on the reaction conditions, including photochromic switching and the synthesis
of polyarenes.
R
3
R
R
X
4
2
3
R
h
1
R
I
R
X
h
R
X
R
2
4
1
N e w p r o d u c ts
X
II
X: CH=CH, O , N, S
In a continuation of our studies on the photochromic properties of diarylethenes we have found a
new skeletal rearrangement resulting in the formation of polycyclic aromatic systems [1]. It was
found that the photoreaction of 1,2-diarylethenes 1 comprising oxazole and phenyl rings under UV
light yields to amido-substituted polyarenes 3 with high efficiency.
O
h
H
(3 6 5 n m )
H
N
N
N
C H C l 3 0 .1 M
Me
O
Ar
Me
1
2
O
Ar
H
Ar
Me
3 (4 5 -8 0 % )
The synthetic features and possible mechanism of the new photorearrangement will be discussed.
Acknowledgments:
This work was financial supported by Russian Foundation for Basic Research (Grant 14-03-31871)
References:
[1] A. G. Lvov, V. Z. Shirinian, V. V. Kachala, A. M. Kavun, I. V. Zavarzin, M. M. Krayushkin.
Org. Lett. 2014, accepted.
201
P91
FRIEDEL-CRAFTS ALKYLATION OF FURANS WITH BENZYL
ALCOHOLS CATALYZED BY COPPER(II) SALTS
A.S. Makarov, M.G. Uchuskin, A.V. Butin
Perm State University, Department of Chemistry, Perm, Russia
Friedel-Crafts reaction is known to be one of the most powerful tool for introduction of variety of
alkyl groups into furan ring, however the use of strong Bronsted acids or hard Lewis acids leads
often to partial destruction of furan substrates due to their acidophobic nature. Nevetheless,
utilization of π-activated alcohols under mild catalytic conditions allows for products to be isolated
in reasonable yields [1]. Various expensive Lewis acids are usually used for activation of alcohols
[2, 3]. Although several benzyl-substituted furans were synthesized by these procedures in
moderate to excellent yields, the substrate scope has not been explored adequately. Thus, the
development of a general catalytic procedure for alkylation of furans with benzyl alcohols
employing inexpensive catalysts remains an important challenge.
Recently we reported a copper vitriol-catalyzed domino-reaction of o-aminobenzyl alcohols with
different furfurylamines which provides a simple route to 2-acylvinyl-substituted indoles [4]. Our
continuing interest in C-C bond forming reactions led us to examine other copper(II) salts in the
alkylation step. We found that some copper(II) salts might be used as catalysts for the alkylation of
furans 2 with substituted benzyl alcohols 1. Resulting benzyl furans 3 were isolated in good to
excellent yields under optimized reaction conditions.
R
1
R
Cu
OH
+
O
R
R
II
R
3
2
1
1
R
2
3
O
2
3
1
R = H , A lk , A lk O , H a l
R 2 = A lk , A r
R 3 = A lk , A r
Herein, we report a novel copper(II)-catalyzed Friedel-Crafts alkylation protocol allowing for
synthesis of a large variety of substituted benzylfurans.
We thank Russian Foundation for Basic Research (RFBR, grant № 14-03-31278) and Ministry of
Education and Science of Russian Federation (4.246.2014/K) for the financial support.
1. M. Bandini, M. Tragni, Org. Biomol. Chem., 2009, 7, p. 1501
2. S. Roy, S. Podder, J. Choudhury, J. Chem. Sci.,2008, 120, p. 429
3. M. Noji et al., Synthesis, 2008, 23, p. 3835
4. Uchuskin M. G., Molodtsova N. V., Lysenko S. A., Strel'nikov V. N., Trushkov I. V., Butin A. V.,
Eur. J. Org. Chem., 2014, p. 2508
202
P92
CATALYTIC CROSS CYCLOMAGNESIATION OF 1,2-DIENES IN THE
SYNTHESIS OF Z,Z-DIENOIC ALCOHOLS AND 5Z,9Z-DIENOIC ACIDS
V.A. Dyakonov, A.A. Makarov, E.Kh. Makarova, U.M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences; Laboratory Catalytic
Synthesys; Ufa; Russia
Intermolecular cross cyclomagnesiation of terminal aliphatic 1 and oxygenated 1,2-dienes 2 was
performed for the first time by means of Grignard reagents and Cp2TiCl2 to give, after acid
hydrolysis of the reaction mixture, oxygenated hydrocarbons containing a 1Z,5Z-diene moiety 4 in
the molecule in up to 94% yields.
The developed reaction formed the basis for elaboration of a new effective method for the synthesis
of 5Z,9Z-dienoic acids, in view of the published data concerning a broad range of biological
activities of these compounds, including, antimalarial, antimicrobial, antitumor, and antiviral
activities. Along with low toxicity of С20-С30 acids, this makes these compounds fairly attractive
as a base for development of modern medical drugs.
We suggested that the developed approach to the synthesis of oxygenated dienes by means of cross
cyclomagnesiation could serve as the basis for a new approach to the synthesis of 5Z,9Z-dienoic
acids.
Thus according to the scheme we proposed, the first step is Cp2TiCl2-catalyzed cross
cyclomagnesiation of terminal aliphatic allenes 6 with the tetrahydropyran ether of hepta-5,6-dien1-ol 5 by EtMgBr under conditions developed above. The subsequent hydrolysis of the reaction
mixture results in oxygenated dienes 7. The removal of pyranyl protection and oxidation of the
5Z,9Z-diene alcohols 8 thus formed leads to target 5Z,9Z-dienoic acids 9 in 45-48% yields and 98%
stereoselectivity.
This work was performed under financial support from the Russian Science Fondation (Grant 1413-00263)
203
P93
CYCLOALUMINATION OF ALKENES AND ALKYNES IN THE
SYNTHESIS OF PHOSPHOLANES AND PHOSPHOLENES
A.L. Makhamatkhanova, V.A. Dyakonov, R.A. Agliullina, U.M. Dzhemilev
Institute of Petrochemistry and Catalysis of RAS, Laboratory of catalytic synthesis, Ufa, Russia
Aluminacyclopentanes 1 and aluminacyclopentenes 2 generated in situ from the cycloalumination
reaction of olefins and acetylenes with Et3Al catalyzed by 5 mol % Cp2ZrCl2 (toluene, ~ 20 оС, 12
h) were found to undergo the phenyl dichlorophosphine-mediated exchange reaction between
aluminum and phosphorus giving rise to practically important 3-alkyl(phenyl)-substituted 1-phenyl
phospholanes 3 and 2,3-dialkyl-substituted 1-phenyl 2-phospholenes 4 in high yields after
hydrolysis of the reaction mixture. The resultant phosphanes 3 and 4 corresponding readily form
oxides and sulfides on treatment with hydrogen peroxide in chloroform or elemental sulfur.
The structure of the synthesized compounds has been established by one- (1H, 13C, Dept 135) and
two-dimensional (HSQC, HMBC и HH COSY) NMR techniques. The effect of the reagent ratio,
duration and temperature of the reaction on the yield of the desired phosphacarbocycles is
discussed.
This work was supported financially by the Russian Foundation for Basic Research (Grants 12-0331259, 14-03-31084) and NSh-2136.2014.3.
1. U.M. Dzhemilev, A.G. Ibragimov, A.P. Zolotarev, R.R. Muslukhov, and G.A. Tolstikov, Bull.
Acad. Sci. USSR, Div. Chem. Sci., 1989, 38, 194.
2. V.A. D’yakonov, Dzhemilev Reactions in Organic and Organometallic Synthesis; NOVA Sci.
Publ.: New-York, 2010, 96 p.
3. U.M. Dzhemilev. Mendeleev Commun., 2008, 18, 1.
204
P94
PIONEERING IONIC LIQUID-PROMOTED NUCLEOPHILIC AROMATIC
CINE-SUBSTITUTION OF HYDROGEN
N.N. Makhova, M.A. Epishina, A.S. Kulikov
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Rissia
The nucleophilic substitution of hydrogen in electron-deficient arenes (SNH) is a general process of
great practical value.1 Over the past decades several variants of SNH processes were opened and
investigated in details: the oxidative nucleophilic substitution of hydrogen, the vicarious
nucleophilic substitution (VNS), the cine- and tele-substitution, the ANRORC substitution. The
cine-substitution is a process, in the course of which the entering nucleophilic group takes up a
position adjacent to that occupied by the leaving group. One of the cine-substitution example is
conversion of substituted nitrobenzenes into benzoic acids under the action of KCN excess in
aqueous EtOH (the von Richter reaction). The carboxylic group always enters in orto-position to
leaving nitro group. This transformation occurs by heating of different substituted nitrobenzenes in
the presence of the KCN excess in refluxing 48% aqueous ethanol during 48-50 h or in a sealed
tube at 150-180 oC during 1-2 h. Yields of final benzoic acids were as a rule low or the expected
benzoic acids were not generated at all. In addition, the reaction is accompanied by a large amount
of acidic tar, apparently polymeric by nature.
In this work we have found that transformation of electron-deficient arenes (nitrobenzene 1a and 4Cl- (1b), 4-Br- (1c), 4-F- (1d), 4-I- (1e), and 4-MeO- (1f) nitrobenzenes) to corresponding benzoic
acids 2a-f under the action of the KCN excess in aqueous EtOH (von Richter reaction) was
promoted by ionic liquids (ILs). Our research team has great expertise and successful experience in
the performance of various reactions in Ils.2 Screening of the conditions for the synthesis of mchlorobenzoic acid 2b from of 4- chloronitrobenzene 1b shown that the optimum molar ratio ionic
liquid [bmim]BF4:1b is 1.75:1 or 175 mol% of [bmim]BF4. All tested cases of the von Richter
reaction of nitroarenes 1a-f in the presence of ionic liquids proved successful and produced those
results which were not possible in before described conditions. The influence of nature of the
substituents in nitrobenzenes on the reaction results was revealed – the stronger electron-donating
properties of substituents, the slower the reaction. This finding is the first case of the nucleophilic
aromatic cine-substitution of hydrogen promoted by ionic liquids.
1. F. Terrier, Modern Nucleophilic Aromatic Substitution; Wiley-VCH, Weinheim, 2013, 488 pp.
2. N. N. Makhova, M. I. Pleshchev, M. A. Epishina, A.S. Kulikov, “Synthesis and transformation
of nitrogen-containing heterocycles in iionic liquids”, Khim Heterocycl, Soedin., 2014 (5), 690703 (in Russian).
This work was supported by Russian Foundation for basic Research (grant 13-03-00153a).
205
P95
REACTIONS OF ADDITION OF THIOPHENOL TO PROPARGYL
SYSTEMS AND BIOCHEMICAL ACTIVITY OF OBTAINED COMPOUNDS
V.M. Farzaliyev, P.Sh. Mammadova, E.R. Babayev, H.Sh. Aliyeva, I.M. Eyvazova
A.M.Guliyev Institute of Chemistry of Additives of Azerbaijan National Academy of Sciences
(ANAS), Beyuk-Shor Str., Block 2062, AZ1029, Baku, Azerbaijan
High reactivity of thiols allows to easily conduct thiylling of multiple carbon-carbon bonds. These
reactions are convenient methods of synthesis of the various derivatives possessing practically
interesting properties, and also they can be considered as modelling ones for some physiologically
important processes occurring in live organisms.
The research of reactions of nucleophylic, radical and non-catalytic addition of aromatic tiols to
acetylene alcohols with account of structure properties of initial reagents gives an opportunity to
establish theoretic bases at purposeful synthesis of practically interesting compounds.
We synthesized phenyl thioalkenols at the condition of nucleophylic, radical and non-catalytic
addition and carried out comparative analysis of results, obtained for all three types of reactions
taking into account structure of initial acetylene alcohols (propargyl, methyl -, dimethyl-, and
methylethylethynilcarbinols) and thiophenol. The basic parameters, such as molar rate of initial
reagents, duration and temperature for these reactions remained to be unchanged.
Isomer content and rate of cis-, trans-conformers were established by H1 NMR-spectra.
Identification of α and β- isomers was carried out on resonance signals of =CH2- and CH=CHgroups , but rate of cis-, trans-conformers was determined by analysis of results of integration with
account of constant of spin-spin interaction. H1 NМR-research of reactionary mixture was carried
out till its separation to exclude the influence of isomer processes as far as possible. Part of βisomer (cis- + trans-) was used as quality measure of influence of factors of initial reagents structure
on regioselectivity. Under these conditions the part of cis-, trans-conformers was the measure of
influence on stereo specificity.
Composition, structure and yield of products of reaction of nucleophylic, radical and non-catalytic
addition of thiophenol to propargyl systems are determined by electronic (to a lesser degree) and
steric factors of the structure of the reacting compounds, mainly, acetylene ones. The direction of
the attack (regiodirectivity) is controlled by space difficulties, formed by both reagents at their
direct interaction, but stereoselectivity depends on the steric factors of the structure, mainly, thiol
compounds.
It has been shown that reaction of non-catalytic addition of arylthiols to propargyl systems is a
convenient and technologically accessible method for purposeful synthesis of arylthio - and
cyclohexylthioamines with high yields. The reaction proceeds, basically, on nucleophylic
mechanism and with partial participation of thiyl radicals.
There has been revealed high antimicrobial effectiveness of series of the synthesized sulphides in
lubricating oils, fuels and cutting liquids.
206
P96
AN EXPERIMENTAL APPROACH FOR THE ESTIMATION OF CRYSTAL
LATTICE ENERGY OF CO-CRYSTAL
A.N. Manin, A.P. Voronin, G.L. Perlovich
G.A. Krestov Institute of solution chemistry of the Russian academy of scienses, "Physical
Chemistry of Drugs" department, Ivanovo, Russia
The creation of pharmaceutical co-crystals is an area of expanding growth. These materials offer a
possible route for the modification of the physicochemical properties of APIs, such as solubility,
physical and mechanical properties, thermodynamic stability etc., without changing the
pharmacological activity. The key design tool used to select a suitable compound (a co-crystal
former) for a given substance is the concept of supramolecular synthon. [1] Several types of
supramolecular synthon are usually realized in two-component crystals and are characterized by
intermolecular hydrogen bonds (H-bonds) of different types and strengths. The energy of these
interactions was evaluated in a number of papers. [2] A lot less attention has been paid to the
quantitative description of the intermolecular interactions of homo- and heterodimers with the
neighbor molecules which play an important role in the successful co-crystal phase formation. The
cumulative characteristic of the intermolecular (noncovalent) interactions in solids is the
sublimation enthalpy ΔHsub. This value extrapolated to 0 K corresponds to the crystal lattice energy,
Elatt. Despite the active investigation of various physicochemical properties of co-crystals, no papers
concerning co-crystal sublimation have been published until now.
The aim of our study is to provide an experimental validation of the transpiration method for cocrystal enthalpy of sublimation estimation. The present research work considers the co-crystal of 2hydroxybenzamide (salicylamide, A) with 4-acetamidobenzoic acid (acetamidobenzoic acid, B).
This co-crystal is chosen for the following reasons. (i) The acid−amide heterosynthon is a persistent
H-bond motif in co-crystal structures. (ii) Salicylamide is an active pharmaceutical ingredient while
acetamidobenzoic acid is safe for human consumption. (iii) The thermodynamic functions of
sublimation for both components have been obtained by us earlier.
A novel 1:1 co-crystal of salicylamide and 4-acetamidobenzoic acid was obtained by DSC
screening procedure as well as grinding (both neat and solvent-drop) and solvent evaporation
techniques. A complete thermal analysis performed by DSC, TG, and hot stage microscopy
revealed that the co-crystal remains stable in its solid form until the melting point at 182.4 °C,
where it breaks down into components. To determine the optimal conditions of single crystal
growth, a triangle phase diagram for the object system with ethanol was built. An X-ray diffraction
experiment with complete solving of the crystal structure was carried out for the co-crystal. For the
first time in literature, the sublimation thermodynamics of a multicomponent crystal was studied
experimentally by the transpiration method in a quasi-equilibrium mode. A presumable mechanism
of the sublimation process was proposed with the heterodimer sublimating and eventually
dissipating into separate molecules.
1. Desiraju, G. R. Crystal Engineering: From Molecule to Crystal. J. Am. Chem. Soc. 2013, 135,
27, 9952−9967;
2. Dunitz, J. D.; Gavezzotti, A. Supramolecular Synthons: Validation and Ranking of
Intermolecular Interaction Energies. Cryst. Growth Des. 2012, 12, 5873−5877;
This work was supported by the Russian Scientific Foundation (№14-13-00640). We thank “the
Upper Volga Region Centre of Physicochemical Research” for technical assistance with DSC and
XRPD experiments.
207
P97
SELECTIVE C-H ALKENYLATION OF ARYL ETHERS AND
THIOETHERS IN MIXTURES
A.N. Marjanov1, K.V. Luzyanin1, V.P. Ananikov2
1 - Laboratory of Cluster Catalysis, Saint Petersburg State University, Universitetsky pr. 26, Stary
Petergof, 198504, Russia
2 - Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47,
Moscow, 119991, Russia
Direct C–H alkenylation of arenes assisted by the directing group represent one of the most atomeconomic approaches for the preparation of 1,2-disubstituted olefines.1–5 While the alkenylation of
single starting material is a well-established strategy, the selective alkenylation of a sole component
in a mixture of substrates, is not known.
A
B
O
S
S
N
2-(phenylthio)pyridine
O
N
Y
2-(phenylsulfinyl)pyridine
S
N
CO2Et
X
mixtures of three or
four substrates
oxidant, catalyst
solvent, D
Y
X
CO2Et
single product
2-phenoxypyridine
benzyl(phenyl)sulfane
Scheme 1. Substrates used for this study (A) and a selective CH alkenylation of a mixture of
substrates with ethyl acrylate (B).
In pursuit of our studies, we discovered that careful optimization of reaction conditions for C–H
alkenylation, e.g. solvent, oxidant, catalyst, reaction temperature and ratio of substrates turns out
possible a selective alkenylation of a single component in a mixture of substrates. Indeed, several
different mixtures of aromatic ethers and thioethers were studied toward ethyl acrylate as
alkenylating source (Scheme 1). For each mixture, only a sole component was a subject of
alkenylation while all others remained intact.
In the current report, we summarize obtained data regarding C–H alkenylation of mixtures of ethers
and thioethers making a particular emphasis on improving the selectivity of the process and
understanding its driving forces.
Acknowledgements: This work has been partially supported by the Saint Petersburg State
University (research grant from Laboratory of Cluster Catalysis), and the Russian Fund for Basic
Research (grant 14-03-01005).
[1] García-Rubia, A.; Fernández-Ibánez, M. A.; Gómez Arrayás, R.; Carretero, J. C. Chem. Eur. J.
2011, 17, 3567–3570. [2] Yu, M.; Xie, Y.; Xie, C.; Zhang, Y. Org. Lett. 2012, 14, 2164–2167. [3]
Zhang, X.-S.; Zhu, Q.-L.; Zhang, Y.-F.; Li, Y.-B.; Shi, Z.-J. Chem. Eur. J. 2013, 19, 11898–11903.
[4] Shi, B.-F.; Zhang, Y.-H.; Lam, J. K.; Wang, D.-H.; Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 460–
461. [5] Liu, B.; Jiang, H.-Z.; Shi, B.-F. J. Org. Chem. 2014, 79, 1521–1526.
208
P98
SYNTHESIS AND CHARACTERIZATION OF DENDRIMERS DERIVED
FROM GLYCEROL
B. Menot, J. Stopinski, S. Bouquillon
Institut de Chimie Moleculaire de Reims CNRS UMR 7312, Universite de Reims Champagne
Ardenne – UFR Sciences Exactes et Naturelles, BP 1039, 51687 Reims Cedex 2 France
For several years, the laboratory was interested in the development of dendrimers using various
organic biosourced by-products, the valuation of which being a real interest for our region. One of
the first explored strategies was based on the decoration of nitrogen-based dendrimers
(commercially available polypropyleneimines (PPIs)) [1] with by-products of glycerin. The toxicity
of these decorated nitrogenous-based dendrimers was evaluated [2] and their potential in catalysis
or in encapsulation demonstrated [1,3].
The synthetic strategy envisaged now by our team is to apply our decoration strategy to
commercially available polyamidoamines (PAMAMs) and to synthesize directly from the glycerin
new families of dendrimers. The preparation of these last dendrimers directly from biobased
building blocks should improve their biodegradation and decrease their toxicity, what is essential
for environmental applications.
The objective of this presentation is to present our preliminary results concerning the development
of these new glycerodendrimers [4].
[1] S. Balieu, A. El Zein, R. De Soussa, F. Jérôme, A. Tatibouët, S. Gatard, Y. Pouilloux, J.
Barrault, P. Rollin, S. Bouquillon, Adv. Synth. Catal. 2010, 352, 1826.
[2] S. Balieu, C. Cadiou, A. Martinez, J.-M. Nuzillard, J.-B. Oudart, F.-X. Maquart, F. Chuburu, S.
Bouquillon, J. Biomed. Mater. Res. Part A 2013 ,101A (3), 613-621.
[3] K. Fhayli, S. Gatard, A. Mohamadou, L. Dupont, S. Bouquillon, Inorg. Chem. Comm. 2013,
27, 101.
[4] B. Menot, J. Stopinski, A. Martinez, S. Bouquillon, publication in preparation.
209
P99
PALLADIUM-CATALYZED HIGHLY REGIOSELECTIVE
PHOSPHONATION OF MESO-UNSUBSTITUTED PORPHYRINS VIA
C(sp2)-H FUNCTIONALIZATION
E.A. Mikhalitsyna, E.S. Podyacheva, I.P. Beletskaya
MSU Faculty of Chemistry, Moscow, Russia
Synthesis of new artificially modified porphyrins has received much attention as a very attractive
and promising goal for catalysis, medicine, light-absorbing materials mimicking the antenna
complexes of photosynthetic system, photovoltaics etc.1 In our work we are focused on the
development and optimization of high regioselective C-H phosphonation of porphyrins and their
metal complexes in meso-position via oxidative Pd(II)-catalyzed dehydrogenative cross-coupling
(CDC). Surprisingly, to the best of our knowledge, there are very few catalytic examples regarding
the C(sp2)–P bond formation through direct phosphonation of the C–H bond with phosphite ester
including a limited class of compounds with acid C-H bond such as coumarins, azoles, terminal
alkynes and α‑ amino ketones.2-5 We herein report the first example of the catalytically oxidative
phosphonation of meso-unsubstituted porphyrins, which has attracted great attention for excellent
atom economy and an enviromentally friendly approach in opposite to classical tremendous
multistep synthesis.6
To study the influence of structural factors on the reactivity of porphyrin substrates the target series
of meso- tris-, di- and mono-mesityl substituted porphyrins and their Ni(II) and Zn(II) metal
complexes were synthesized by condensation of corresponding dipyrrylmethanes with
mesitylaldehyde in the presence of an acid catalysts and oxidant.7 Pd(II)-catalyzed C-H
posphonation of Ni(II) 5-mesitylporphyrin (NiPMes) was successfully carried out with 40 mol%
Pd(OAc)2 as catalyst, 1.2 eq. of 4,4’-bipyridine as ligand, 6 eq. of K2S2O8 as oxidant and excess of
diethyl phosphite in refluxed dioxane under air atmosphere during 24 hours (Fig. 1). Target monophosphotated product were obtained and separated by column chromatography in good 80% yield
along with 14% of bis-phosphonated product. The same conditions were used for phosphorylation
of bis-5,10-dimesityl and tris-5,10,15-trimesitylporphyrins to prepare in 42% and 29% mono- and
diphosphonated porphyrins correspondingly.
Fig. 1. Pd-catalyzed C-H phosphonation of 5-mesitylporphyrin
1. J. Mack, Z. Shen, N. Kobayashi. In Handbook of Porphyrin Science; Kadish, K. M., Smith, K. M., Guilard, R., Eds.;
World Scientific Publishing: Singapore, 2012; Vol. 23, pp. 281−373.
2. X. Mi, M. Huang, J. Zhang, Ch. Wang and Y. Wu, Organic Letters, 2013, 15, pp. 6266–6269.
3. Ch. Hou, Yu. Ren, R. Lang, X. Hu, Ch. Xia and F. Li, Chem. Commun., 2012, 48, pp. 5181–5183.
4. Y. Gao, G. Wang, L. Chen, P. Xu, Y. Zhao, Y. Zhou and L.-B. Han, J. Am. Chem. Soc., 2009, 131, 7956-7957.
5. B. Yang, T.-T. Yang, X.-A. Li, J.-J. Wang and S.-D. Yang, Org. Lett., 2013, 15, 19, 5024–5027.
6. Yu. Y. Enakieva, A. G. Bessmertnykh, Yu. G. Gorbunova, Ch. Stern, Y. Rousselin, A. Y. Tsivadze and R. Guilard,
Organic Letters, 2009, 17, pp. 3842-3845.
7. Ch. Brückner, J. J. Posakony, C. K. Johnson, R. W. Boyle, B. R. James and D. Dolphin, J. Porphyrins
Phthalocyanines, 1998, 2, pp. 455–465.
210
P100
SYNTHESIS AND REACTIVITY OF 7-AMINO-4-OXO-3-R-8-R’-6HPYRAZOLO[5,1-C][1,2,4]TRIAZINES
L.M. Mironovich, D.V. Shcherbinin, A.Y. Podolnikova
Southwest State University, Basic Chemistry and Chemical Technology, Kursk, Russia
Reactivity of the 1,2,4-triazine derivatives containing pyrazole ring in the structure is now
intensively studied. 7-Amino-4-oxo-3-R-8-R’-6H-pyrazolo[5,1-c][1,2,4]triazines (2,3) has been
synthesised by refluxing compound (1) with malononitrile and ethyl cyanoacetate in the medium
pyridine [1].
Boiling of compound (2) with KOH in the alcoholic medium has led to hydrolysis with isolation of
compound (4), it was treated with HCl and received pyrazolo[5,1-c][1,2,4]triazine-8-carboxylic acid
(5). Decarboxylation at high temperatures leads to isolation of compound (6). Pyrazolo[5,1c][1,2,4]triazine-8-carbohydrazide (7) obtained by boiling compound (2) with N2H4 in the alcoholic
medium.
Refluxing of compound (3) in the alkaline medium has led to carbamide (8).
Boiling of compound (8) with
formic acid has led to pyrimido[4’,5’:3,4]pyrazolo[5,1c][1,2,4]triazines (10). The structure of compound (10) was determined by X-ray crystallography.
For fant of reflux P2S5 in pyridine with compound (10) leads to 4,11-dithioxo-3-R-6H,10Hpyrimido[4’,5’:3,4]pyrazolo[5,1-c][1,2,4]triazine (11)
and
11-oxo-4-thioxo-3-R-6H,10Hpyrimido[4’,5’:3,4]pyrazolo[5,1-c][1,2,4]triazine (12). N-(3-tert-butyl-4,8-dithioxopyrazolo[5,1c][1,2,4]triazin-7-yl)аmid metadithiophosphorous acid (9) (348 [M+]), was received from the
responding compounds (3).
The structures of the synthesized compounds are confirmed with spectral methods (IR, H1-NMR-,
mass spectra) and elemental analysis data.
Compounds show weak antimicrobial activity.
[1] Mironovich, L.M. and Kostina, M.V. // Russian Journal of Organic Chemistry, 2011, vol. 47,
№12, P. 1917.
211
P101
HYBRID MATERIALS BASED ON COPPER AND PALLADIUM
COMPLEXES OF (1,10-PHENANTHROLYL)PHOSPHONATES FOR
CATALYSIS
A.Yu. Mitrofanov1, A.G. Bessmertnykh-Lemeune2, R. Guilard2, N.S. Goulioukina1, I.P.
Beletskaya1
1 - A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, 31-4 Leninskiy p.,
Moscow, 119071, Russia
2 - Institut de Chimie Moleculaire de Universite de Bourgogne (ICMUB), UMR CNRS 6302, 9
avenue A. Savary, 21078, Dijon Cedex, France
Considerable attention has been attached recently to the immobilization of transition metal
complexes onto solid supports to prepare advanced catalytic systems [1]. Using this approach, it is
expected to increase catalyst stability and allow for catalyst recycling and product separation.
Organophosphonates are of interest for this field due to their simple synthesis and high reactivity
towards various metal salts and alkoxides. In fact, different ligands can be easily decorated by the
phosphonate group for immobilization onto thermally and mechanically stable metal oxide
matrices. Herein we describe the results of our studies on the functionalization of titania by
copper(I) and palladium(II) complexes with (1,10-phenanthrolyl)phosphonates (Pphen) recently
described by us (Figure)[2].
Figure. Copper(I) and palladium(II) complexes with Pphen.
The covalent grafting of the complexes was performed according to two routes. The first one, socalled ‘‘one-pot’’ synthesis, involves a co-condensation step between a complex with an inorganic
precursor (titanium isopropoxide) according to the sol-gel technique. In the second one, so-called
‘‘post-functionalization’’, а chemical surface modification of a preformed mesoporous titanium(IV)
dioxide (SBET = 650 m2/g) through chemical bonds between the hydroxyl groups covering the pore
surface and complexes is used. The structural and textural properties of these hybrid materials will
be presented and explained based on a solution behavior of the studied complexes. High catalytic
activity of newly synthesized hybrid materials in the palladium-free Sonogashira reaction, the
copper-catalyzed boration of alkynes and Suzuki reaction are reported and examples of catalyst
recycling are given.
Acknowledgements: This work was carried out in the frame of French-Russian Laboratory
“LAMREM” of CNRS and RAS and supported by Russian Foundation for Basic Research (grant
#12-03-93114).
[1] Suib, S. L. New and Future Developments in Catalysis, Elsevier: Amsterdam, 2013.
[2] (a) Mitrofanov, A. Yu., Bessmertnykh-Lemeune, A., Stern, C., Guilard, R., Gulyukina, N. S.,
Beletskaya, I. P. Synthesis, 2012, 44, 3805. (b) Mitrofanov, A. Yu., Manowong, M., Rousselin
Y., Brandes S., Guilard, R., Bessmertnykh-Lemeune, A., Chen, P., Kadish, K. M.,
Goulioukina, N., Beletskaya, I. Eur J. Inorg. Chem., 2014, DOI:10.1002/ejic.201402161.
212
P102
SYNTHESES, STABILITIES AND REACTIVITIES OF
ALKYNYL(ARYL)IODONIUM SALTS
W.J. Moran
University of Huddersfield, Department of Chemistry, Huddersfield, UK
Iodonium salts are increasingly popular reagents in organic synthesis because of the range of useful
reactivities that they exhibit.1 The most investigated iodonium salts are the diaryliodonium salts,
which can, in principal, donate either of their aryl groups in reactions with nucleophiles (Scheme
1).2 In contrast, alkynyl(aryl)- and alkenyl(aryl)iodonium salts only donate the alkyne or alkenyl
groups respectively. This means that the aryl iodide group is, essentially, a spectator group in these
two types of iodonium salts. However, the effect of changing this spectator group on the reactivity
of these salts has not been studied.3
Scheme 1. General reactivities of iodonium salts with nucleophiles highlighting the “spectator” role
of the aryl iodide in alkenyl- and alkynyl(aryl)iodonium salts
Our study on the preparation of a range of alkynyl(aryl)iodonium salts directly from terminal
alkynes and aryl iodides and the stabilities and reactivities of these salts will be discussed. 4
Surprisingly, we found a marked increase in the stability and reactivity of iodonium salts derived
from 2-iodoanisole (Scheme 2). I will also present our results on generating alkynyl(aryl)iodonium
salts from alkynylsilanes and reacting them directly resulting in yield augmentations of up to 50%
compared to the iodobenzene parent.
Scheme 2 Direct syntheses of alkynyl(aryl)iodonium salts and the effect of the aryl iodide
substituents on stabilities and reaction yields
1. For reviews of iodonium salts in organic synthesis, see: a) M. S. Yusubov, A. V. Maskaev, V. V.
Zhdankin, Arkivoc, 2011, i, 370; b) E. A. Merritt, B. Olofsson, Angew. Chem., Int. Ed., 2009, 48, 9052; c)
T. Okuyama, Acc. Chem. Res., 2002, 35, 12.
2. M. Fujita, E. Mishima, T. Okuyama, J. Phys. Org. Chem., 2007, 20, 241.
3. Selected examples of reactions with alkynyl(phenyl)iodonium salts: a) B. L. Williamson, P. J. Stang, A.
M. Arif, J. Am. Chem. Soc., 1993, 115, 2590; b) B. L. Williamson, R. R. Tywinski, P. J. Stang, J. Am.
Chem. Soc., 1994, 116, 93; c) M. Ochiai, K. Miyamoto, T. Suefuji, S. Sakamoto, K. Yamaguchi, M.
Shiro, Angew. Chem. Int. Ed., 2003, 42, 2191; examples of reactions with alkenyl(phenyl)iodonium salts:
d) M. G. Suero, E. D. Bayle, B. S. L. Collins, M. J. Gaunt, J. Am. Chem. Soc., 2013, 135, 5332; e) T.
Okuyama, M. Fujita, Acc. Chem. Res., 2005, 38, 679.
4. D. J. Hamnett, W. J. Moran manuscript submitted for publication.
213
P103
MATHEMATICAL MODELING OF DYNAMICS OF PHOTOCHEMICAL
REACTIONS AT THE QUANTUM AND THE CLASSICAL DESCRIPTION
OF THE RADIATION FIELD
V.A. Morozov, N.D. Chuvylkin, E.A. Smolenskii
N. D. Zelinsky institute of organic chemistry, Leninsky prospekt, 47, 119991 Moscow, Russia
Are examples of differences between the results of using two methods of mathematical modeling of
dynamics of populations of the states of the molecule in photochemical reactions. The first method
is based on the solutions of the Schrodinger equation for the probability amplitudes of the
population of states of the molecule and the radiation field is described by quantum theory. When
using a three-level model of the molecule, these solutions are obtained analytically. The second
method is based on numerical solutions of the equations for the density matrix elements of the
molecule interacting with the classically described irradiation and phenomenological decay of
excited states of molecules. The differences formalisms used methods and an underlying
conceptions of the physical sense of the light transformation by molecules in photochemical
reactions are discussed.
214
P104
SYNTHESIS OF SPIROCYCLOPROPYL MALONYL PEROXIDE FROM
CYCLOPROPYL MALONIC ESTER
O.M. Mulina, V.A. Vill, A.O. Terentiev
N.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Laboratory for
Studies of Homolytic Reactions, Moscow, Russia
Cyclic diacyl peroxides were in use in oxidation reactions in the 1950-70s [1]. At the present time,
great attention is attracted to these compounds [2]. An unique property of such spirocyclic
diacylperoxides as malonyl and phtaloyl ones is their capability to oxidate unsaturated compounds
without any catalysts alternatively to their linear analogues, for example commercially available
benzoylperoxide and succinylperoxide, and widespread peroxy cycles: ozonides and tetraoxanes.
Among malonyl peroxides a spirocyclopropyl malonyl peroxide is the activest and the most
frequently used oxidant. It has the lowest molecular weight among familiar malonyl peroxides [2a],
and this fact makes the oxidation process more atom-efficient.
The main procedure of synthesis of spirocyclopropyl malonyl peroxide 2 is the reaction of
spirocyclopropyl malonic acid with 90-98 % hydrogen peroxide [3] or hygrogen peroxide and urea
hydrogen peroxide [2a] in the presence of methanesulfonic acid (Scheme 1).
In the present work we succeeded in synthesis of peroxide 2 in the reaction between
spirocyclopropyl malonic peroxide 1, which can be easily synthesised by alkylation of diethyl
malonic ester with 1,2-dichlorethane in high yields 85-88 %, and hygrogen peroxide and urea
hydrogen peroxide in the presence of methanesulfonic acid.
This method makes the synthesis of spirocyclopropyl malonyl peroxide 2 dramatically easier,
because it excludes come chemical and procedural steps.
1. (a) W. Adam, J. W. Diehl., J. Chem. Soc., Chem. Commun., 1972, 13, 797-798. (b) C. L. Perrin,
T. Arrhenius, J. Am. Chem. Soc., 1978, 100, 5249-5251.
2. (a) J. C. Griffith, K. M. Jones, S. Picon, M. J. Rawling, B. M. Kariuki, M. Campbell, N. C. O.
Tomkinson, J. Am. Chem. Soc., 2010, 132, 14409-14411. (b) M. Schwarz, O. Reiser. Angew.
Chem. Int. Ed., 2011, 50, 10495-10497. (c) C. Yuan, A. Axelrod, M. Varela, L. Danysh, D.
Siegel, Tetrahedron Lett., 2011, 52, 2540-2542.
3. (a) W. Adam, R. Rucktäschel, J. Am. Chem. Soc., 1971, 93, 557-559. (b) M. J. Darmon, G. B.
Schuster, J. Org. Chem., 1982, 47, 4658-4664.
215
P105
HYPOTHETICAL REACTION MECHANISM OF H2-ASSISTED N-C6H14DENOX OVER Ag/Al2O3 CATALYSTS
A.I. Mytareva, N.A. Sadokhina, G.N. Baeva, A.Yu. Stakheev
N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
Since Satokawa et al. [1] discovered that the low temperature activity of Ag/Al2O3 in HC-SCR of
NOx can be boosted by addition of small amounts of H2, the nature of “hydrogen effect” has been
studied intensely. However the mechanism of H2-assisted HC-SCR of NOx is still debated and
several solutions have been proposed. One of the possible pathways involves H2-promoted
formation of NO3‾ surface species, followed by their transformation to reactive NO2‾ species, which
further react with activated HCs. In the present study in order to evaluate possible contribution of
this pathway into overall H2-assisted HC-SCR over Ag/Al2O3, we compared the rate of H2-assisted
C6H14 DeNOx in steady-state and the rate of NO3‾surf. reduction by C6H14 in the presence and the
absence of H2.
It was repeatedly shown by FTIR and TPD that addition of H2 into reaction mixture results in the
intensive formation of NO3‾surf., located on Ag species and Al2O3 surface. This process is very fast
and leads to the complete removal of NOx from the reaction mixture until saturation of the catalyst
surface is attained. Surface reaction of NO3‾surf. species with the feed containing 1000 ppm C6H14
revealed their inertness with respect to HC reductant. On the other hand surface reaction with NO or
H2 leads to NO3‾surf. → NO2‾surf. transformation as evidenced by intensive NO2 evolution, and in situ
XPS data. It should be noted that NO was found to be more effective in NO3‾surf. → NO2‾surf.
transformation, as compared to H2, particularly at the reaction temperature below ~ 180°C.
Transformation of NO3‾surf. into NO2‾surf. greatly enhances reactivity of surface N-containing
species, and NO2‾surf. species are rapidly reduced into N2 in the course of the surface reaction with
300 ppm C6H14 + 1000 ppm H2. It was found that the rate of NO3‾surf. reduction by hydrocarbons in
the presence of H2 is identical to the rate of H2-HC-SCR of NOx in steady state. This observation
suggests significant contribution of NO3‾surf. reduction in the rate of the overall HC-SCR mechanism
at 150-300 °C. These results appear to be in a good agreement with the literature data on the
transient measurements of H2-assisted DeNOx over Ag/Al2O3 [2-3].
References:
[1] S. Satokawa// Chem. Lett., 2000, 29, 294
[2] J.P. Breen, R. Burch and C.J. Hill// Catal. Today, 2009, 145, 34
[3] S. Chansai, R. Burch, Ch. Hardacre, J. Breen and F.J. Meunier// J. Catal., 2010, 276, 49
216
P106
DEPENDENCE OF THE SPECIFIC ACTIVITY ON THE PLATINUM
PARTICLE SIZE IN THE DEEP OXIDATION OF C1 - C6 NORMAL
ALKANES
A.M. Batkin1, A.Yu. Stakheev1, I.E. Beck2, N.S. Teleguina1, G.O. Bragina1, V.I. Zaikovsky2, Yu.V.
Larichev2, V.I. Bukhtiyarov2
1 - N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
2 - Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
The deep oxidation of volatile organic compounds (VOCs) over supported catalysts based on noble
metals (Pt, Pd) is among the main exhaust gas aftertreatment technology for mobile machinery and
stationary applications. One of the most important factors influencing the efficiency of noble metal
catalyst is the size of metal particles. High Pt dispersion improves utilization of noble metal since
increases the fraction of atoms accessible for a reaction. On the other hand, very small metal
particles may be ineffective in the reactions requiring multi-atomic surface active sites (structuresensitive reactions). The influence of the metal particle size on the total and specific catalytic
activity (SCA, or atomic activity) in deep oxidation was extensively studied. A comparison between
experimental data obtained by independent authors allowed us to suppose that the structural
sensitivity of deep oxidation and the size effect of the platinum particles on the specific catalytic
activity can also be dependent on the structure (first of all, on the size) of the hydrocarbon
molecule.
In this study we compared the effect of Pt particle size on the activity in catalytic combustion of
normal alkanes with different hydrocarbon chain length (C1 – C6) over a series of 0.8% Pt/Al2O3
with different average Pt particle sizes ranging from 1 to 12 nm.
It was established that the range in which specific catalytic activity changes depends substantially
on the carbon chain length of the n-alkane. In the oxidation of CH4 or С2H6, atomic activity
increases approximately 2– 3 times as the Pt particle size changes from 1 to 11 nm. In propane
oxidation, SCA increases approximately by a factor of 5–6, whereas in the oxidation of n-C4H10 and
n-C6H14, the specific activity increases 20 and 25 times, respectively. Thus, the structural sensitivity
of the deep oxidation of n-alkanes increases with an increase in the size of the hydrocarbon
molecule being oxidized.
It was found that the catalysts with the maximum degree of dispersion of platinum (dPt = 1–2 nm)
exhibit the highest total activity in the oxidation of small molecules. The catalysts consisting of
larger Pt particles (3–6 nm) are most active in the oxidation of longer n-butane and n-hexane
molecules, whereas the activity of the finer catalysts is substantially lower.
Acknowledgement: Financial support by RFBR grant # 12-03-01104-a is gratefully acknowledged
217
P107
COMPOSITE CATALYSTS [Fe-BETA + REDOX] FOR COMBINING
CATALYTIC PROCESSES: 1) NH3-SCR AND NH3-SLIP REMOVAL,
2) NO TO NO2 OXIDATION AND FAST SCR
A.I. Mytareva1, G.N. Baeva1, D.A. Bokarev1, A.Yu. Stakheev1, P. Selvam2
1 - N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
2 - Indian Institute of Technology-Madras, National Centre for Catalysis Research and Department
of Chemistry, Chennai, India
Combining several catalytic processes over single catalyst is the general trend in modern
heterogeneous catalysis. We explored this approach to develop catalytic systems for environmental
protection – selective catalytic reduction of NOx by ammonia (NH3-SCR). NH3-SCR is of
theoretical and practical interest for abatement NOx emission from automotive (diesel engines) and
stationary (power plants) sources. Recently, NH3-SCR can be achieved by using catalytic systems
based on Fe-Beta or Cu-Beta. However, these catalysts have two main drawbacks: 1) insufficient
NOx conversion at “cold-start” condition (150-250ºC), and 2) NH3-slip problem due to incomplete
conversion or exhaust temperature upswings. We attempted to solve these problems by using
composite catalysts [Fe-Beta + RedOx] comprising NH3-SCR and RedOx functions.
1. Combining NH3-SCR and NH3-slip removal
According to our recent results Fe(Mn)MCM-48 can be used as RedOx components due to high
activity in NH3 oxidation process. Therefore composite catalyst was prepared by mechanical mixing
of Fe-Beta and Fe(Mn)MCM-48 components.
It was shown that mechanical mixing of Fe-Beta with Fe(Mn)MCM-48 allowed us to combine
favorable NH3-SCR performance of Fe-Beta (1) and activity of Fe(Mn)MCM-48 in NH3
oxidation (2) in one catalytic brick.
2 NO + 2 NH3 + ½ O2 → 3 H2O + 2 N2
– over Fe-Beta
(1)
4 NH3 + 3 O2 → 2 N2 + 6 H2O
– over Fe(Mn)MCM-4
(2)
Varying the ratio of the components, optimum SCR and NH3-slip removal performance of
composite catalyst can be achieved. Moreover [Fe-Beta + Fe(Mn)MCM-48] demonstrates low N2O
emission.
2. Combining NO oxidation and NH3-SCR
CeO2-ZrO2 demonstrates high activity in NO oxidation to NO2. Furthermore, it was found, that the
activity can be further boosted, viz. modification by manganese. In this study Mn/CeO2-ZrO2 was
mixed with Fe-Beta for enhancing low-temperature NH3-SCR activity of zeolite component.
It was found that mixing of zeolite and RedOx component leads to a significant increase in NO x
conversion at 150-250ºC. This synergistic effect can be attributed to combination of two processes:
NO oxidation over Mn/CeO2-ZrO2 (3) followed by the Fast SCR (4) on Fe-Beta.
2 NO + O2 → 2 NO2
– over Mn/CeO2-ZrO2
(3)
NO + NO2 + 2 NH3 → 3 H2O + 2 N2
– over Fe-Beta
(4)
Acknowledgments
This work was supported by the Russian Foundation for Basic Research (Grant: 13-0392711/IND_a) and Department of Science and Technology, New Delhi (Grant: INT/RUS/RFBR/P152).
A. Mytareva is grateful to Haldor Topsøe A/S for financial support in the framework of Ph.D.
student support programme.
218
P108
NON CATALYTIC EFFICIENT APPROACH TO SUBSTITUTED 2,3,4,9TETRAHYDRO-1H-XANTHEN-1-ONES - A GROUP OF ORALLY ACTIVE
NEUROPEPTIDE Y Y5 RECEPTOR ANTAGONISTS FROM
SALICYLALDEHYDES AND DIMEDONE
R.F. Nasybullin, O.O. Sokolova, M.N. Elinson
N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
Functionally substituted tetrahydro-1H-xanthen-1-ones have received considerable attention in the
field of medicinal chemistry due to their useful biological properties and applications [1]. Recently
it has been found that tetrahydro-1H-xanthen-1-ones are orally active and selective Y5 antagonists
[2]. Known methods for the synthesis of tetrahydro-1H-xanthen-1-ones have its merits and suffer
from disadvantages such as long reaction times, moderate yields or complicated work-up
procedures. Thus, the development of an efficient and facile method for the synthesis of tetrahydro1H-xanthen-1-ones is in high demand.
In the present study we report our results on thermally induced non catalytic transformation of
salicylaldehydes and dimedone into substituted tetrahydro-1H-xanthen-1-ones (Scheme 1). The
reaction is performed in ethanol under 3 min reflux. Corresponding 9-(2-hydroxy-4,4-dimethyl-6oxo-1-cyclohexen-1-yl)-3,3-dimethyl-2,3,4,9-tetrahydro-1H-xanthen-1-ones were formed in
excellent 85-95% yields.
Scheme 1
In conclusion, simple non catalytic system can produce, under neutral conditions, a very fast
(3 min) and selective transformation of salicylaldehydes and dimedone into tetrahydro-1H-xanthen1-ones –– the orally active and selective Y5 antagonists and the promising heterocyclic compounds
for different biomedical applications. The procedure utilizes simple equipment; it is easily carried
out and is valuable from the viewpoint of environmentally benign diversity-oriented large-scale
processes.
Acknowledgements
The authors gratefully acknowledge the financial support of the Russian Foundation for Basic
Research (Project No. 14-03-31918).
References
1. H. K.Wang, S. L. Morris-Natschke, K. H. Lee, Med. Res. Rev., 1997, 17, 367.
2. S. Mashiko, A. Ishihara, H. Iwaasa, H. Sano, Z. Oda, J. Ito, M. Yumoto, M. Okawa, J Suzuki, T.
Fukuroda, M. Jitsuoka, N. R. Morin, D. J. MacNeil, L. H. T. Van der Ploeg, M. Ihara, T.
Fukami, A. Kanatani, Endocrinology, 2003, 144, 1793.
219
P109
SOLUBILITY AND STRUCTURE OF CHITOSAN IN AQUEOUS MEDIA OF
VARIOUS ACIDITY. MOLECULAR DYNAMIC STUDY
V.S. Naumov, S.K. Ignatov, A.G. Razuvaev, A.E. Mochalova, I.A. Glazova, L.A. Smirnova
N.I. Lobachevsky State University of Nizhny Novgorod, Russia
Polyaminoglucanes, particularly, chitosan (poly-1,4-(N-acetyl)-β-D-2-glucopyranoseamine) are
considered today as promising means for encapsulating the protein-contaning drugs ensuring their
transport inside an organism. This task is, however, complicated by the lack of information about
the structure of the chitosan complexes in aqueous solutions, their thermodynamic properties and
kinetics of complexation. In particular, the structure of chitosan chains in the aqueous solution
based on the data of electron microscopy was a subject of discussion [1]. Data on the complexation
constants with various protein agents are virtually absent, and the details of dissolution kinetics are
mostly studied on the basis of formal kinetic approach or without adrressing to the protonation
effects [2,3]. In the present study, we use the molecular dynamics (MD) simulations in order to
elucidate the details of nanocrystalline chitosan dissolution, the influence of amino group
protonation, and kinetics of its dissolution at various acidity of aqueous media. The model system
was a chitosan nanocrystal surrounded by the water molecules (SPC water model) and counterions
(Cl-) compensating the protonated amino group charges. The simulation box size was 12.4 x 11.7 x
20.8 nm (~302000 atoms in total, ~100000 water molecules). The nanocrystal was consisted of 8
chains of 20 monomeric units (3.2 kDa per chain). The initial crystal structure was constructed on
the basis of XRD data [4]. Some of amino groups were protonated in the crystal with the
protonation degree (PD) corresponded to the pH values from 5.3 to ~7.2. Calculations were
performed with GROMACS 4.6.1 using the force field GROMOS 53A6Carbo [5], specially
improved for better polyaminoglycane unit description. Force field modification was perfromed on
the basis of quantum chemical calculations (HF/STO-3G//B3PW91/6-31++G(d,p)). Simulation
period was up to 10 ns with integration step of 1 fs in the NVT-ensemble at 300K, controlled by the
Berendsen thermostat. It was found that, at the beginning of dissolution process, the nanocrystal
undergoes the remarkable twist-like deformation resulting to the compact bunches of chitosan
chains. Then, at PD>0.3, the bunches undergo slow dissociation which rate is determined by the
quantity of protonated amino groups. The time-dependency of dissolution degree (measured as an
average distance between chains) is almost linear during 10 ns of simulations. The dissolution rate
estimated as the time derivative of average distance between chains is also linearly dependent on
PD, with threshold of dissolution about PD=0.3 (pH~6.8) which agrees well with available
experimental data. The final structures of chitosan after 10 ns of dissolution in aqeous media of
various acidity are shown in Figure.
[1] Pedroni V.I., Schulz P.C., Gschaider M.E., Andreucetti N. Colloid Polym Sci, 2003, 282, 100.
[2] Franca E.F., Lins R.D., Freitas L.C.G., Straatsma T.P. J. Chem. Theory Comput, 2008, 4, 2141.
[3] Franca E.F., Freitas L.C.G., Lins R.D. Biopolymers, 2011, 95, 448.
[4] Yui T., Imada K., Okuyama K.,Obata Y.,Suzuki K.,Ogawa K. Macromolecules, 1994. 27, 7601.
[5] Hansen H.S., Hünenberger P.H. J Comput Chem, 2011, 32, 998.
This work was supported by the RFBR (Project No. 14-03-00585, 14-03-31981)
220
P110
THE STEAM OSMOTIC ENGINE WITH THE INCREASED EFF TO 50%
P.A. Nazarov
Russian Chemical Technology University named after D.I. Mendeleev,Chair of Processes and
devices of chemical technology position,Moscow.Russia
The evolution of heat osmotic engine [2] on the prototype[1] is to increase the temperature
(T1=380С) of the left part of the circuit(fig.1) the engine in changing the phase state of the water
from liquid to gas, but also adding a second stage of desalination by electrodialysis.
Due to the process "steam" or osmosis process of rapid diffusion of water vapor molecules through
the membrane into the liquid solution inside the reactor 3(fig.1) osmosis increases the specific
power of the engine(W/kgengine), as well as its efficiency.
Steam osmotic engine[2] repeats energy cycle thermal power plant, but through a process of
"steam" osmosis and because of the lack of vapor condensation (in the cooler) its efficiency is much
higher.
Ideal efficiency manual 2-nd Carnot's theorem is(fig.1):
EFF= [(T1–T2)/T1]х100% = [(380С–20С)/380С]х100%=[(653–293)/653]х100%=55%
(1)
Given the mechanical losses in the pump Pump1, 2; formula for calculating the efficiency takes the
form.
EFF мах ={(N–Wpumps)/∆Q}= [(T1–T2)/T1]–Wpumps= [(P1osmosis–P2reverse osmosis)/P1osmosis]–Wpumps (2)
Where N [W] - output power of osmotic (hydraulic) flow ∆Pturbines=224,1at; ΔQ [W] - The amount
of heat in heat generators 1,2 to keep the system in a given thermal regime (the left side of the
technological scheme T1=380C=653k, right side T2=20C=293k); Wpumps [W] - power pumps1,2.
Steady state operation of the scheme of steam osmotic engine T1=379-380C, T2=20-40C.
fig.1
References
1. Patent of USA №4193267 on 18.03.1980, Metod and apparatus for generating power utilizing
pressure-retarted osmosis. Inventor Sydney Loeb, the Bulletin, №1877989, 15.02.1978.
2. The application for the patent of the Russian Federation №2014108948 from 11.03.2014,
«Method of reception of mechanical energy and the steam osmotic engine for its realisation» / the
applicant and the legal owner Nazarov P. A.
221
P111
THE UNSATURATED CARBON-CARBON BOND HYDROGENATION IN
PRESENCE OF NANOPARTICLES OF THE Fe-Ni GROUP
D.N. Nebykov, V.M. Mokhov, Yu.V. Popov
Volgograd State Technical University, Chemical Technology Faculty, Volgograd, Russia
The hydrogenation of unsaturated substances and arenes is a widely used industrial process, but it
proceeds in harsh conditions or requires using of expensive catalysts. We discovered some methods,
giving an ability to carry out the reduction of different substituted alkenes and arenes without using
of high temperatures and pressures or expensive materials by means of using ferrous, cobalt or
nickel nanoparticles as catalysts.
The advantage of methods is in combination of metal nanoparticles synthesis and organic substance
hydrogenation. The nano-catalyst is formed from inexpensive metal salts by their reduction with
complex borohydrides or alumohydrides or by hydrazine hydrate in solutions, in some cases
proceeds in situ hydrogenation of unsaturated bonds.
The essential interest deserves a method of liquid phase alkenes hydrogenation with gaseous
hydrogen at atmospheric pressure, which is a widely used and inexpensive industrial reagent. Using
of simply obtained from accessible and inexpensive substances metal nanoparticles is able to
decrease the cost and energy losses comparing to traditional hydrogenation methods.
The investigations showed an ability of the carbon-carbon unsaturated bond hydrogenation at very
smooth conditions - atmospheric pressure and near room temperatures. Also was found that change
of hydrogenating agent, catalyst and it's preparing conditions makes possible to direct the process
selectivity and also to reduce some functional groups. As starting materials for hydrogenation were
used different derivatives of norbornene, styrene, linear and cyclic alkenes, heterocyclic
compounds.
References
1. Colloid and nanodimensional catalysts in organic synthesis: I. Investigation of hydrogenation
selectivity of unsaturated compounds with hydrazine hydrate and aluminum hydride / Popov
Yu.V., Mokhov V.M., Nebykov D.N. // Russian Journal of General Chemistry. - 2014. - Vol. 84,
No. 3. - C. 444-448.
2. Colloid and nanodimensional catalysts in organic synthesis: II. The hydrogenation of alkenes
with hydrogen at atmospheric pressure / Popov Yu.V., Mokhov V.M., Nebykov D.N. // Russian
Journal of General Chemistry. - 2014. - Vol. 84, No. 4. - C. 622-628.
3. Hydrogenation of unsaturated carboxylic acids/ Mohov V.N., Popov Y.V., Nebykov D.N.//
Izvestiya VolGTU, Series “Chemsitry and technology of organoelemnt monomers and polymeric
materials” Iss 12. Mezhvus.sb.nauch.st./VolGTU. – Volgograd, 2014, N7 (134) – C. 60-63.
222
P112
SYNTHESIS AND INVESTIGATION OF FUNGICIDAL ACTIVITY OF 6BROMO-4-HYDROXY-2-PHENILINDOLE
O.D. Neverova, M.D. Dutov, S.A. Shevelev, G.V. Bastrakova, O.V. Serushkina, K.E. Aisina, S.V.
Popkov
N. D. Zelinsky institute of organic chemistry, Leninsky prospekt, 47, 119991 Moscow, Russia
Recently, we showed high fungicidal activity of the 2-aryl-4-hydroxy-6-nitroindoles [1]. The
presence of the nitro group in these compounds, of course, reduces their value as fungicides, as in
the case of use as agricultural agents, and in the case of drugs. Therefore it is very important task to
replace the nitro group to an appropriate electronegative substituent, as which, by analogy with
Arbidol, we have chosen a bromine atom. Synthesis of the title compound (1) was carried out as
follows:
It is shown that 6-bromo-4-hydroxy-2-phenylindole outperforms standard triadimefon by
fungitoxicity with respect to all the examined fitopatagence not inferior nitro analog.
Compound
Triadimefon
Mycelium growth inhibition, % (С = 30 μg mL-1)
V.i.*
R.s.
F.o.
F.m.
B.s.
S.s.
100
92
88
100
95
100
89
100
88
100
100
100
42
66
60
79
71
47
The authors thank the Russian Foundation for Basic Research (Grant No 13-03-01276) for financial
support
[1] G. V. Kokurkina, M. D. Dutov, S. A. Shevelev, S. V. Popkov, A. V. Zakharov and V. V.
Poroikov, European Journal of Medicinal Chemistry, 2011, 46, 4374-4382.
223
P113
THEORETICAL STUDY OF MULTISTEP MECHANISM OF THERMAL
FRAGMENTATION OF O-NITRO TOLUENE
E.V. Nikolaeva, A.G. Shamov, G.M. Khrapkovskii
Kazan National Research Technological University, Catalisis Department, Kazan, Russia
A mechanism which is believed to be involved in thermodistruction of o-nitrotoluene (I) and other
nitroarenes bearing hydrogen-containing substituent in ortho-position to nitro group, includes the
formation of its aci-form at the first step. At the same time, significant differences in activation
enthalpies ( H = Ea – RT) of thermodistruction of compound I were observed by different authors.
Thus, in the temperature interval 300-350оС H equals 172,8 kJ/mol[4]; 350-420оС H =
201,6 3 kJ/mol; 797-907оС H = 206,2 kJ/mol. Results of theoretical investigation of the
thermodistruction mechanism of compound I, can be presented as the following scheme:
The data on relative enthalpies of formation of transition states of reactions ( Hf , enthalpy of
formation of o-nitrotoluene was selected as zero) for this scheme provided in the literature suggest
that it should terminate at the limiting step of hydrogen atom transfer between two oxygens in the
group =N(O)OH (process III VI). Possibility of further reactions remained unclear. The
investigation of the specified sequence of transformation of o-nitrotoluene by B3LYP/631+G(2df,p) demonstrated that this scheme can be realized if isomerization III
IV proceeds as a
rotation of =N(O)OH around С=N bond. For this process, Hf equals 188 kJ/mol. The limiting
steps are elimination of water (V
VII) or hydroxyl radical (V
VI) from 2,1-benzisoxazol2(3H)-ole (V), with barriers being equal 193,0 and 204,9 kJ/mol, respectively. That is, at lower
temperatures, a more probable would be the realization of the process V
VII, since for it Hf
correlates well with experimental estimation of 201,6 3 kJ/mol. At higher temperatures, there is an
opportunity for elimination of OH from compound V (V
VI), since for it Hf correlates well
with experimental estimation of 206.2 kJ/mol. In favor of this conclusion is the systematic character
of deviations (1-9 kJ/mol decrease) of calculated values of activation enthalpies of primary act and
specified steps from experimental data.
1. V.G. Matveev, V.V. Dubihin, G.M. Nazin, Izv. Acd. Nauk USSR. Ser. chem., 2, 474-476 (1978).
2. G.M.Khrapkovskii, A.G.Shamov, E.V.Nikolaeva, D.V.Chachkov, Russ.Chem.Rev., 78, 10, 903-943
(2009).
3. Y. Y. Maksimov, Zh. Phys. Chem., XLIII, 3, 725-729 (1969).
4. T.B. Brill, K.J. James, Chem. Rev., 93, 2667-2692 (1993).
5. W. Tsang, D. Robaugh, W.G. Mallard, J. Phys. Chem., 90, 5968-5973 (1986).
6. Y.V. Il’ichev, J. Wirz, J. Phys. Chem. A., 104, 7856-7870 (2000).
7. S.C. Chen, S.C. Xu, E. Duau, M.C. Lin, J. Chem. Phys. A., 110, 10130-10134 (2006).
8. G. Fayet, L. Joubert, P. Rotureau, C. Adamo, J. Phys. Chem. A., 113, 13621-13627 (2009).
9. E.V. Nikolaeva, D.V. Chachkov, A.G. Shamov, G.M. Khrapkovskii, Vestnik NovGU, 2, 73, 76-82 (2013).
224
P114
OPTICAL ACTIVE BIS-IMINE RHODIUM(I) COMPLEXES IN TRANSFER
HYDROGENATION OF PROCHIRAL C=O BONDS
L.O. Nindakova, A.V. Khatashkeev, N.M. Badyrova, I.A. Ushakov, E.Kh. Sadykov
Irkutsk State Technical University, Physical-technical Institute, Irkutsk, Russia
Rhodium (1+) complexes with bis-aldimine ligands on the basis of (R,R)-1,2-cyclohexanediamine
(1) were tested in the asymmetric transfer hydrogenation of ketones and ketoacids, with
isopropanol as hydrogen source under basic conditions. The catalyst:substrate ratio was 1/170-340.
Ligands (1а-1с) were synthesized by the condensation reaction of diamine 1 with aldehides: 2pyridinecarbaldehyde, 2-quinolinecarbaldehyde and 2-thiophene-carbaldehyde, following the
scheme:
,
R’- =
Rhodium complexes were used as catalysts for this reaction, it was confirmed by 1Н and 13С HMR
that this complexes were formed in situ from the reaction of [Rh(1,5-COD)Cl]2 and ligands 1a-1с.
TOF and TON values are higher for ligands that synthesize from 2-pyridinecarbaldehyde (250 h-1;
340) and from 2-quinolinecarbaldehyde (109 h-1; 170); the lowest values were obtained for bisaldimine based on 2-thiophene-carbaldehyde (16 h-1; 43). The excess formation of R-(+)enantiomer of 1-phenylethanol and R-(-)-methyl mandelate is observed for all Rhodium complexes.
But the all used catalytic systems are slightly enantioselective (prior to 20 % of ee), similar result
was obtained using Ir - and Ru -bis(oxazoline) catalytic system [1].
[1] Gömez M, Jansat S., Muller G., Bonnet M. C., Breuzard J. A.J., Lemaire M. J. Organomet.
Chem, 2002, 659, 186-195
225
P115
STRUCTURAL ANALYSIS OF IODINE ADDUCTS WITH
HETEROAROMATIC N-OXIDES
V.V. Romanov1, Y.P. Nizhnik1, A.V. Ryzhakov2, L.L. Rodina3
1 - Petrozavodsk State University, Petrozavodsk, Russia
2 - Karelian Research Center RAS, Petrozavodsk, Russia
3 - St. Petersburg State University, St. Petersburg, Russia
Heteroaromatic N-oxides contain two potential donor centers capable to interact with Lewis acids
such as halogen bond donors: -system of the aromatic rings and the oxygen atom of N-oxide
group. According to the HSAB principle, the iodine as a soft Lewis acid might interact on both
donor centers, however the literature and our IR-spectroscopy data unambiguously indicate the
oxygen atom as a donor center.
Yet a half-century ago T. Kubota [1] questioned the exact geometry of iodine adducts of N-oxides
due to potentially different hybridization types of oxygen atom. Actually, owing to an ambivalent
character of the group N–O in the heteroaromatic N-oxides, the oxygen atom’s hybridization might
be characterized by the two extreme cases – sp3 or sp2.
Single X-ray data obtained by us for the adducts of iodine with pyridine, 4-methylpyridine and 4chloroquinoline N-oxides have clearly demonstrated the sp3-character of the oxygen atom in the
complexes and the absence of any
-interaction. In the both cases for pyridine N-oxides, the
structure of the adducts includes infinite quasi one dimensional chains of alternating D and A
moieties: ( I–I O I–I O ). In the case of the adduct of 4-chloroquinoline N-oxide with iodine
(see the picture), the individual adduct molecule may be distinguished within the crystal lattice. To
estimate the possibility of existing different conformations of the adduct (sp3 or sp2), on the base of
its crystal structure the energy profile of the structure was calculated in Hyperchem program as the
dependence of the potential energy on the dihedral angle (I–I–O–N) – (quinoline ring):
Two distinct barriers have been observed: at 0o ( E = 357 Kcal/mol, corresponds to the structure
where iodine is in a close proximity to H8), and 180o ( E = 3.7 Kcal/mol, iodine is in a close
proximity to H2). The real X-ray structure (dihedral angle 117 o, ( E = 0.25 Kcal/mol) is similar to
the calculated conformer (dihedral angle 131 o, ( E = 0 Kcal/mol)). Obtained data indicate that
potential “sp2-stereoisomers” are not favorable energetically due to probably the sterical factors and
should not be observed at least in the case of “strong” adducts with bulky Lewis acids.
[1] T. Kubota // J. Amer. Chem. Soc. 1965. 87(3). P.458-468.
226
P116
COPPER CATALYZED CYCLOPROPYL-ALLYLIC RING-OPENING
TRANSFORMATIONS OF GEM-CHLOROFLUORO- AND GEMBROMOFLUOROCYCLOPROPANES. PREPARATION OF 2FLUOROALLYL HALIDES
M.A. Novikov, N.V. Volchkov, M.B. Lipkind, O.M. Nefedov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russian
Federation
Cyclopropyl-allylic ring-opening transformation of gem-chlorofluoro- and gem-bromofluorocyclopropanes widely available by carbene cyclopropanation of corresponding alkenes is an
attractive tool for preparation of 2-fluoroallylic compounds that are known to possess a wide range
of biological activities.
Ability of copper(I) compounds to catalyze cyclopropyl-allylic isomerization of gem-chlorofluoroand gem-bromofluorocyclopropanes was found and an effective route to 2-fluoroallyllic chlorides
and bromides was developed.
F
R1
R3
R2
R4
CFX
R1
R2
F
X
R3
R4
C u X /M e C N
or
(N H C )C u X /d io x a n e
R1
X
R2 R3
R4
8 0 -1 0 0 ° C
X = C l, B r;
R 1 -R 4 = H , C H 3 , -(C H 2 ) n - (n = 2 -4 ), P h , -C H = C H 2 , c -C 3 H 5 , C l;
Thus, from alkyl-, aryl, chloro substituted gem-chlorofluoro- and gem-bromofluorocyclopropanes,
their bicyclic and spiro-substituted derivatives, in presence of CuX or (NHC)CuX (NHC — Nheterocyclic carbene) in MeCN or 1,4-dioxane at elevated temperatures corresponding 2fluoroallyllic chlorides and bromides could be prepared. In the case of vinyl substituted gemchlorofluorocyclopropane 5-chloro-2-fluoropenta-1,3-diene forms as a major product. Isomerization
of gem-chlorofluoro-1,1’-bi(cyclopropane) proceeds via successive opening of both cycles leading
to 6-chloro-2-fluorohexa-1,3-diene as an only product.
References
1) N. V. Volchkov, M. A. Novikov, M. B. Lipkind, and O. M. Nefedov, Mendeleev Commun.,
2013, 23, 19–21;
2) M. A. Novikov, N. V. Volchkov, M. B. Lipkind, and O. M. Nefedov, Russ. Chem. Bull., 2013,
62, 71–82.
227
P117
DESIGN, SYNTHESIS AND BIOLOGICAL EVALUATION OF PGLYCOPROTEIN INHIBITORS FOR MODULATION AND PREVENTION
OF MULTIDRUG RESISTANCE
M. Sagnou1, X. Alexiou1, E.S. Kolotova2, A.A. Shtil2, A.A. Zeifman3, I.J. Titov3, O.V. Stroganov3,
V.V. Stroylov3, I.V. Svitanko3, F.N. Novikov3, G.G. Chilov3
1 - Demokritos National Research Center, Greece
2 - Russian Scientific Oncology Center RAS
3 - N. D. Zelinsky institute of organic chemistry, Russia
Multidrug resistance (MDR) mediated by P-glycoprotein (one of ATP-binding cassette (ABC)
transporters) through efflux of antineoplastic agents from cancer cells is a major obstacle to
successful cancer chemotherapy. The inhibition of P-glycoprotein (P-gp) is thus a logical approach
to circumvent MDR. There has been intensive research effort to design and develop novel inhibitors
for the P-gp and other ABC transporters to achieve this goal. Complex in silico P-gp inhibition
model was developed in the present study using the pharmacophore ensemble/support vector
machine scheme (to take into account the promiscuous nature of P-gp), molecular docking and
molecular dynamics approach (to predict ligand binding pose in huge P-gp hydrophobic cavity) and
free energy perturbation methods (FEP, to accurate estimation of ligand-binding affinities). Two
series of novel P-gp inhibitors (based on curcumine scaffold) was designed, synthesized and
evaluated in doxorubicin accumulation and cytotoxicity tests on chronic myeloid leukemia cell line
К562/Dox with MDR phenotype.
During the first round of optimization we discovered novel P-gp inhibitors that bind to the active
site of the enzyme and have activity comparable to clinical P-gp blocker verapamil. We showed that
that hydrogen bonds with residues T837 and Q737 and hydrophobic and stacking interactions with
residues P770, Y307 and P994 play significant role in ligand binding. We demonstrated that for
correct predictions of relative binding energy by FEP it is necessary to carry out an explicit account
of the solvent, since the bridging water molecules significantly contribute to the energy of
formation of the protein-ligand complex.
In the second round of optimization we discovered P-gp inhibitors that were to verapamil and
comparable with P-gp inhibitors in clinical trials. We demonstrated that these compounds do not
exhibit the toxicity at concentrations up to 50 uM and have more than 100-fold lower IC50 in
doxorubicin cytotoxicity tests on К562/Dox with MDR phenotype
228
P118
SELECTIVE HYDROGENATION OF UNSATURATED ALDEHYDES ON
THE COMPOSITE Pt-BASED NANOCATALYSTS. A QUANTUM
CHEMICAL STUDY
A.I. Okhapkin1, O.B. Gadzhiev1, A.E. Masunov2, S. Kunz3, M. Bäumer3, S.K. Ignatov1
1 - N.I. Lobachevsky State University of Nizhny Novgorod, Chemistry Department, Nizhny
Novgorod, Russia
2 - University of Central Florida, Chemistry Department, Orlando, USA
3 - University of Bremen, Institute for Applied and Physical Chemistry (IAPC), Bremen, Germany
Selective hydrogenation of unsaturated aldehydes to alcohols is a key process in fabrication of
fragrance components for the modern cosmetology and perfume industry. Since the selective oxogroup hydrogenation is thermodynamically unfavorable due to the presence of the C=C bond, the
industrial process is indirect, complicated, and expensive. Recently, a novel type of catalyst was
proposed that shows enhanced selectivity towards unsaturated alcohols. It is using metal-oxide
supported Pt-nanoparticles with chemically modified surface. In a present work, the elementary
steps of such a catalytic reaction, i.e., propenal and croton aldehyde hydrogenation, were studied
within the cluster models of Pt surface using the DFT quantum chemical calculations (BLYP and
PBE density functionals in conjunction with the CRENBS or LANL2DZ pseudopotentials for Pt
atoms and 6-31G(d,p) basis set for the remaining atoms). The clusters Pt8, Pt13, and Pt25 consisting
of two layers of Pt atoms were used as models for the Pt nanoparticle surface. The diameter of the
Pt25 cluster is about 12 Å which is close to the size estimated for the experimentally studied Pt
nanoparticles (18±3Å) [1]. The different spin states of the clusters were considered (spin
multiplicity up to 11). The adsorption of reagents (H2 and aldehydes) and the organic ligands
working as orienting agents ensuring the reaction selectivity (BuSH, Bu = n-C4H9) were studied as
initial steps of the catalytic process. The various kinds of adsorption were studied: (1) physical
adsorption of H2 on different sites of Ptn clusters; (2) dissociative chemisorption of H2 resulting in
the Pt-adsorbed H atoms; (3) chemisorption of ligands forming the Ptn-SBu structures and the
neighboring –SBu/H adsorbed pairs; (4) aldehyde adsorption on the neat Pt surface and the surface
partially occupied by the H atoms and the –SBu and –SBu/H groups. For all these pre-reaction
surface complexes, the molecular structures, adsorption energies, and vibrational frequencies were
studied. It was found that the ground state of the Pt25 clusters is the quintet one with the typical
spread of energies in lower spin states (M=1,3,5, and 7) of about 3 kcal mol-1. The H2 physical
adsorption energy is about 0.6-1.8 kcal mol-1 depending on the adsorption site. The dissociative
adsorption energy of H2 was estimated to be 5-9 kcal mol-1which is in reasonable agreement with
experimental values (~16 kcal mol-1)[2]. At the same time, the –SBu group formation energy was
estimated as 30-56 kcal mol-1 depending on the adsorption site. Their estimated surface coverage of
about 4/9 monolayer is in reasonable agreement with the experimentally observed dependence of
hydrogenation kinetics on the surface coverage [1]. The kinetic barriers of the surface migration of
adsorbed H atoms and various hydrogenation pathways are discussed on the basis of the different
theoretical estimates.
1.
L. Altmann, S. Kunz, M. Bäumer, J. Phys. Chem. C 2014, 118, 8925-8932
2.
P.R. Norton, J.A. Davies, T.E. Jackman, Surf. Sci., 1982, 121, 103-110
The work was partially supported by the Russian Foundation for Basic research (project No. 14-0300585). OBG and AIO are thankful to DAAD for the travel grants support.
229
P119
NMR DIFFERENTIATION OF CHIRAL ALCOHOLS AND AMINES USING
SELENIUM-BASED CHIRAL PROBES
N.V. Orlov, V.P. Ananikov
Zelinsky Institute of Organic Chemistry RAS, Russia, Moscow, Leninsky pr. 47, 119991
Modern NMR spectroscopy is a powerful tool for structure elucidation of complex organic
molecules including natural products1. An important issue in this field is analysis of complex
mixtures of chiral compounds and determination of enantiomeric composition of each individual
molecule. Utilization of chiral auxiliary reagents allows to efficiently differentiate enantiomers in
NMR spectra2. Besides, continuous progress in development of chiral auxiliaries and derivatization
protocols made it possible to obtain diastereomers suitable for NMR analysis within minutes
directly in NMR tube excluding isolation and purification steps3. Nevertheless analysis of mixtures
of several chiral compounds is still a complicated task4.
Recently we have developed simple synthetic routes to several selenium-based chiral probes which
readily react with chiral alcohols and amines directly in an NMR tube (Scheme 1, left) followed by
determination of their enantiomeric composition using 77Se NMR spectroscopy5. In this case only
signals of selenium-containing diastereomers formed are observed in the spectra thus simplifying
assignment procedure.
Scheme 1. DCC-promoted "in tube" derivatization of chiral alcohols and amines with chiral probes
R-ArSePA (left) and examples of spectral data - structure relationship using R-(4chlorophenylselanyl) propionic acid (right).
Now we have revealed that the diastereomers formed can be efficiently differentiated in 77Se NMR
spectra depending on the nature of substituents at stereogenic center of analyzed chiral aclohols and
amines (Scheme 1, right). This observation gives possibility to perform preliminary structure
elucidation in several minutes and to analyse complex mixtures using a single 1D NMR experiment.
Scope and limitations of this approach to various chiral alcohols and amines will be presented in the
poster.
Acknowledgments: This work was supported by RFBR (project No. 12-03-01094).
1. Breton, R. C.; Reynolds, W.F. Nat. Prod. Rep. 2013, 30, 501.
2. Wenzel, T. J. Top. Curr. Chem. 2013, 341, 1.
Chem. Rev. 2012, 112, 4603.
4. Novoa-Carballal, R.; Fernandez-Megia, E.; Jimenez, C.; Riguera, R. Nat. Prod. Rep. 2011, 28,
78.
5. Orlov, N. V.; Ananikov, V. P. Chem. Commun. 2010, 46, 3212.
230
P120
NEW LIFE FOR OLD REACTION. SYNTHESIS OF THIAZOLIDINES VIA
REGIOSELECTIVE ADDITION OF UNSYMMETRIC THIOUREAS TO
MALEIC ACID DERIVATIVES
A.S. Pankova, M.A. Kuznetsov
Saint Petersburg State University, Insitute of Chemistry, Saint Petersburg, Russia
Thiazolidine derivatives and, in particular, thiazolidinylacetic acids are highly valuable scaffolds for
medicinal and bioorganic chemistry as can be exemplified by a central penicillin core that contains
fused -lactam and thiazolidine rings. Various substituted thiazolidines feature exclusively broad
range of biological activities that warrants a constant interest in preparing new thiazolidines and
studying their properties.
Addition of thiourea derivatives to maleic anhydride or maleimides is used to get a rich
functionalized thiazolidinylacetic acid framework. This reactions is classical, but at the same time
many questions concerning regioselectivity in case of unsymmetric thioureas remained unclear and
there were problems to be solved. Some controversial data and surprising results can be found in the
literature and therefore we decided to thoroughly investigate factors governing the regioselectivity
of this process.
We have shown that addition of N-aryl-N’-ethyl(or methyl)thioureas to N-arylmaleimides proceeds
regioselectively
providing
2-(3-ethyl(methyl)-2-arylimino-4-oxo-1,3-thiazolidin-5-yl)-Narylacetamides in good yields. It is applicable for a wide range of substituents in aromatic rings and
the product selectivity does not depend on the solvent used. A remarkable dependence of the
reaction regioselectivity on the solvent polarity was revealed with more sterically hindered alkyl
thioureas. In nonpolar benzene 3-alkyl-2-arylimino-4-oxo-1,3-thiazolidines are formed
preferentially, whereas in polar isopropyl alcohol and acetonitrile the reaction regioselectivity
changes in favor of 2-alkylimino-3-aryl-4-oxo-1,3-thiazolidines. In the case of the most bulky
N-tert-butyl-N’-phenylthiourea, the isomer with exo-cyclic position of an alkyl group is formed
exclusively. At the same time addition of sterically hindered N-alkyl-N’-arylthioureas to maleic
anhydride leads only to 3-alkyl-2-arylimino-4-oxo-1,3-thiazolidinylacetic acids independent of the
solvent used. We have unambiguously established the structures of all obtained thiazolidines (some
of them using X-ray data) and demonstrated the utility of the 15N-1H HMBC spectroscopy for their
unequivocal assignment.
Authors thank the Russian Scientific Fund for a research grant no. 14-13-00126.
231
P121
MECHANISTIC STUDY OF Cu2O AND CuO-CATALYZED C–S CROSS
COUPLING REACTION
Y.S. Panova1, V.P. Ananikov2
1 - Saint-Petersburg State University Institute of Chemistry, Russia, Petrodvorets, Universitetsky
pr. 26
2 - N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Russia, Moscow,
Leninsky pr. 47
C-S cross-coupling is a valuable synthetic tool to prepare a diversity of sulfur derivatives with high
yields [1,2]. In spite of various synthetic applications, the mechanism of C-S cross-coupling was not
clearly resolved. Catalytic reactions mediated with CuO and Cu2O nanoparticles represent a
substantial challenge in this regard.
In order to have a better insight of the reaction pathways, detailed FE-SEM, ESI-MS and NMR
studies were carried out. Ligand-free copper oxides (I, II)-catalyzed reactions of thiophenol with 4iodotoluene were chosen as a model reaction. The role of copper centers on the surface of the
nanoparticles and in solution was studied and compared to reported in the literature reaction
pathways.
It is interesting to note, DFT calculations revealed that strongly polar solvent (like DMSO)
facilitates the formation of the anionic active species [Cu(SPh)2]- [3]. This type of intermediates is
favored for halogen atom transfer mechanism as its activation energy barrier much lower (33.2
kcal/mol), then the activation energy barrier of the most often suggested oxidative addition
mechanism (41.3 kcal/mol), according to theoretical study [3].
Based on calculations and experimental data we will discuss the following catalytic pathways: 1)
generation of [Cu(SPh)2]- complex by reaction of thiophenol with the base and copper oxides; 2)
iodine atom transfer from 4-iodotoluene to Cu-center to form the [Cu(SPh)I]- intermediate and
phenyl radical; 3) attack by phenyl radical at S atom of Ph-thiolate affording the formation of
coupling product. It is noteworthy, that in the absence a base, intermediate [CuI2]- was observed by
ESI-MS analysis.
References
[1] S. Ganesh Babu, R. Karvembu Tetrahedron Lett., 2013, 54, 1677–1680.
[2] S.-W. Cheng, M.-C. Tseng, K.-H. Lii, C.-R. Leec, and S.-G. Shyu Chem. Commun., 2011, 47,
5599–5601.
[3] S.-L. Zhang, and H.-J. Fan Organometallics, 2013, 32, 4944-4951.
Acknowledgment
P.Y. acknowledges
(12.50.1560.2013).
Saint-Petersburg
State
232
University
for
postdoctoral
fellowship
P122
TRANSFORMATIONS OF CYCLIC ORGANIC PEROXIDES IN THE
PRESENCE OF TRANSITION METALS
Z.Y. Pastukhova1, I.A. Yaremenko1, L.G. Bruk2, A.O. Terent’ev1
1 - N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
2 - Lomonosov Moscow State University of Fine Chemical Technologies
Currently, organic peroxides are produced by dozens of the largest chemical companies in a largetonnage scale. Peroxides are the main source of free radicals in chemical practice. They are widely
used to initiate radical including chain-radical processes, especially in the polymer manufacture. In
the past decades, the chemistry of organic peroxides has attracted considerable attention from
physicians and pharmacologists due to the detection of these compounds high antimalarial,
anthelminthic and antitumor activities.
Thermal instability of peroxides, because of the presence of weak O-O bonds, leads to
decomposition at normal or elevated temperatures. Transition metals (Fe, Сu, Мn, Со, Сr) and their
salts are effective catalysts of decomposition. Usually decomposition of organic peroxides is
nonselective process. Decomposition reactions are not limited by the only homolytic decomposition
of O-O bond resulting in a complex product mixture is generated.
In our work we found the selective transformations of cyclic organic peroxides in the presence of
transition metals (Scheme 1).
Scheme 1. Transformations of Cyclic Organic Peroxides
O O
?
O O
Mn+
O
?
O O
?
O O
This work is supported by RFBR №14-03-00237.
Terent’ev A.O., Yaremenko I.A., Chernyshev V.V., Dembitsky V.M., Nikishin G.I. // J. Org. Chem.
2012, 77, 1833-1842.
Terent'ev A.O, Yaremenko I.A., Vil' V.A., Dembitsky V.M, Nikishin G.I. // Synthesis. 2013, 45 (2),
246-250.
Ingram K., Yaremenko I.A., Krylov I.B., Hofer L., Terent'ev A.O., and Keiser J. // J. Med. Chem.
2012, 55 (20), 8700-8711.
233
P123
ENANTIOSELECTIVE HYDROLYSIS OF 3-HYDROXY-1,4BENZODIAZEPIN-2-ONE ESTERS BY PIG LIVER MICROSOMES
V.I. Pavlovsky1, E.A. Shesterenko1, I.I. Romanovska1, O.V. Sevastyanov1, T.A. Yurpalova1, S.A.
Andronati1, V.Ch. Kravtsov2
1 - A.V. Bogatsky Physico-chemical Institute, National Academy of Sciences of
Ukraine, Lustdorfska dor., 86, Odessa, Ukraine
2 - Institute of Applied Physics, Academy of Sciences of Moldova, Chisinau, Republic
of Moldova
The configuration of chiral biologically active compounds plays an important role in processes of their
biotransformation and binding with biomembranes. Methods of asymmetric synthesis and resolution of
enantiomers are fraught to difficulties, thus development of economical preparative biotechnological
methods of enantiomers resolution is prospective.
Carboxylesterase (EC 3.1.1.1) is the most studied enzyme, which catalyze the enantioselective hydrolysis of
a wide range of acyclic, carbocyclic and heterocyclic compounds. But the number of publications, devoted to
the enantioselective hydrolysis of benzodiazepine derivatives, which clinical effects include anxiolytic,
anticonvulsant and hypnotic effects, muscle relaxation is quite limited.
The aim of the present work was the development of a method of the enantioselective hydrolysis of 3hydroxy-1,4-benzodiazepin-2-one esters by pig liver microsomes and investigation of S-enantiomers binding
affinity for central benzodiazepine receptors.
Microsomal fraction was isolated by the low speed centrifugation method in the presence of Ca2+ ions.
Protein yield was 38.0 mg/g of liver tissue and esterase activity was 17.25 U/mg protein.
The method of enantioselective hydrolysis of 1-unsubstituted-(1), 1-methyl-(2), 1-ethyl-(3) 3-acetoxy-7bromo-5-phenyl-1,2-dihydro-3H-1,4-benzodiazepin-2-ones
using pig liver microsomal fraction was
3
developed (esterase activity 130- U/cm ; pH 7,0; t 37 ºC; τ 2,5 h; DMSO concentration 40 % (v/v)).
Enantiomers of 3-hydroxy-1,4-benzodiazepin-2-one esters were purified by silica gel column
chromatography. Enantiomeric excesses of substrates (ees) were determined by HPLC using Shimadzu LC8A pump with a chiral column ChiraDex. It was shown, that the products of the reaction – 1-unsubstituted(4), 1-methyl-(5), 1-ethyl-3-hydroxy-7-bromo-5-phenyl-1,2-dihydro-3H-1,4-benzodiazepin-2-ones (6)
underwent racemization during hydrolysis and subsequent isolation, what is consistent with the literature
data [1].
The S-enantiomers of three substrates 1S-3S were obtained with ees >97 % and yields 44-49 %, their
absolute configurations were determined by X-ray crystallography (fig.).
3S(b)
1S
2S
3S(a)
Fig. ORTEP view of molecular structure of 1S, 2S, and two conformers in the structure 3S (a and b)
illustrates their absolute configuration.
Values of specific rotation 20D of 1S-3S were +116.9º, +195.3º, +193.8º (c = 1.0, CHCl3), respectively.
With a help of the radioligand binding methods, affinity of S-enantiomers 1S-3S and racemates 1-3 for the
CBR of rat brain was determined and values of IC50 were evaluated. It was shown, that the S-enantiomers
1S-3S are 1.4-2.1 times more potent ligands of CBR than the corresponding racemates 1-3.
References:
1. Oswald P., Desmet K., Sandra P. et al, 2002 Determination of the enantiomerization energy barrier of some 3hydroxy-1,4-benzodiazepine drugs by supercritical fluid chromatography. J. Chromatogr. B. 779, 283–295.
234
P124
A SIMPLE TECHNIQUE FOR PRODUCING PALLADIUM
NANOPARTICLES ON CARBON SUPPORT AS CATALYST FOR
CROSS-COUPLING REACTIONS
E.O. Pentsak, V.P. Ananikov
N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia
Recently, much attention has been paid to carbon materials, modified by metal nanoparticles, due to
increasing interest in using of such systems in catalysis, material science optics and electronics.
Successful application of palladium nanoparticles supported on carbon materials was facilitated
many organic synthesis procedures. Efficiency and selectivity of these catalysts was determined by
such characteristics as particles size, the uniformity of their distribution on the support surface and
the range of particle size distribution.
We have previously shown that the labile behavior in solution and the tendency to form palladium
clusters are inherent in Pd2dba3 complex [1]. Thus, we were able to cover carbon material by
nanoparticles with optimum sizes and high monodispersity under mild conditions without the need
of stabilizers and reducing agents, using easily available Pd2dba3 complex as a precursor of
palladium.
In this study, we found that the variation of temperature and concentration of solution allowed
tuning of coverage density of the supported nanoparticles, as well as control of diameter of the
nanoparticles from 2 to 15 nm. This procedure was found scalable and well reproducible.
Dispersion values of the nanoparticles sizes usually did not exceed 1-2 nm. Kinetics of the process
was investigated by nuclear magnetic resonance spectroscopy NMR and scanning electron
microscopy (FE-SEM). Study of deposition process by FE-SEM showed that the average particles
size was stabilized quickly during the coating process. The particles size depended on the
conditions of the process, while the increase of the coating density occurred gradually until
complete consumption of the Pd precursor.
The catalytic activity of prepared palladium nanoparticles supported on graphite has been studied
utilizing model Suzuki and Heck reactions. The catalyst prepared by our method showed high
efficiency for this type of reactions, 100% conversion of the Heck and Suzuki reactions was reached
only in a few hours at low catalyst loadings (0.2-0.5 mol %).
[1] Zalesskiy S. S., Ananikov V. P. // Organometallics, 2012, V. 31, P. 2302–2309.
235
P125
SELECTIVE CLEAVAGE OF GLYCOSIDIC LINKAGES USING
SOLVOLYSIS WITH ANHYDROUS TRIFLUOROACETIC ACID
S.N. Senchenkova, A.V. Perepelov, A.V. Filatov, A.S. Shashkov, Y.A. Knirel
N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
A common approach in structural studies of polysaccharides is the selective cleavage of glycosidic
linkages to give oligosaccharide fragments, which usually show better-resolved NMR spectra than
the parent polymer and are readily amenable to MS analysis. One of the methods useful for this
purpose is solvolysis with strong acids. For instance, solvolysis with anhydrous HF has been used in
structural analysis of carbohydrates since early 1980s, and later trifluoromethanesulfonic (triflic)
acid was introduced. However, these reagents have some disadvantages; e.g. HF handling requires
special equipment, triflic acid is expensive, and both are highly hazardous. In search for a better
solvolytic agent, we tested anhydrous CF3CO2H in selective cleavage O-polysaccharides of
medically important bacteria Escherichia coli and Enterobacter cloacae and found it to be useful
and convenient. CF3CO2H split selectively the α1→2- and α1→3-rhamno- and -fuco-pyranosidic
linkages as well as the HexpNAc-(1→4)-Manp linkage, whereas other linkages were not affected.
Below are structures of the cleaved O-polysaccharides (O68 at 50°C for 16 h; all others at 40°C for
5 h) with the glycosidic linkages sensitive to CF3CO2H shown in rectangles.
236
P126
СROSS-COUPLING OF TEREPHTHALONITRILE DIANION AND
AROMATIC NITRILE RESULTING IN SUBSTITUTED DICYANOBIARYLS
R.Yu. Peshkov1, E.V. Panteleeva1, V.D. Shteingarts2
1 - Novosibirsk State University, Novosibirsk, Russia
2 - N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Novosibirsk, Russia
Cyanobiaryls have a wide area of practical utilization in technology (polymers, semiconductors,
OLED) as well as in medicine [1]. Modern approaches to their synthesis are based on manifold
cross-coupling reactions of preactivated arenes catalyzed by transition metals. We suggest a concise
and inexpensive non-catalytic approach applying terephthalonitrile dianion 1 as cyanoarylating
reagent for neutral aromatic nitriles. It was found that 1, generated by terephthalonitrile reduction
with alkali metal in liquid ammonia, undergoes cross-coupling with benzonitrile as well as 2- and 3cyanobiphenyls providing 4,4`-dicyanobiphenyl and dicyanoterphenyls [2]. Present work is aimed
on broadening the scope of neutral substrates applicable for such type of cross-coupling and study
of its mechanism by revealing electronic and structural factors governing regioselectivity and
efficiency of the reaction. For the purpose we varied the nature of substrate by introduction of an
extra substituent into benzonitrile (Me, MeO, F, Cl, Br) as well as by alteration of aromatic moiety.
(cyanonaphthalenes, 9-cyanoanthracene, 4-cyanopyridine). Besides nitriles, electron-deficient
arenes: ethylbenzoate, 3-methylbenzophenone and nitrobenzene were tested. Also experimental and
quantum-chemical modeling of possible reaction pathways were performed. We found out that
benzonitriles substituted with o-, m-Me, -MeO and -F, both cyanonaphthalenes and 9cyanoanthracene undergo coupling with 1 providing subsequent cyanobiaryls (scheme). Towards all
other substrates 1 acts as reducing reagent. The regularities revealed are interpreted in terms of the
reaction scheme with the intermediacy of the charge-transfer complex 2 between 1 and cyanoarene
[2], which further transforms into dimeric dianion 3 either by heterolytic pathway or by successive
single electron transfer and recombination of primary generated radical anions. Subsequent
decyanation of 3 forms long-living monoanion 4 capable to be converted into cyanobiarylic product
either through oxidation or alkylation.
CN
CN
CN
CN
X
CN
CTC
1
X
CN
CN
X
CN
Bu
X
CN
F
NC
CN
-CNCN
CN
4
3
X
CN
F
X
[O]
Alk
NC Alk
heterolytic pathway (SNAr)
F
2-
CN
X
X
X
primary RA-pair
2
+
CN 2M
ArX
in-cage
recombination
ET
2-
2- +
CN
CN
CN CN *
CN
AlkB
r
-Br -
X
Bu
CN
X
-H+
-CN-
CN
CN
CN
CN
NH3
CN
M: Li, Na, K
X: H; 2-, 3-CH3;
-OCH3; -F
ArX:
CN
CN
CN
CN
CN
F
F
F
CN
CN
F
X
CN
CN
F
F
cyanobiaryle
yield 14-90%
CN
NC
CN
CN
CN
CN
F
CN
CN
CN
CN
CN
CN
X
F
The financial support of the CMSD of RAS (the project No 2.6) is acknowledged.
[1] Corbet, J.-P., Mignani, G. Chem. Rev., 2006, 106, 2651.
[2] a) Panteleeva, E.V. et al., Eur. J. Org. Chem., 2005, 2558; b) Panteleeva, E.V. et al.,
ARKIVOC, 2011, viii, 123.
237
P127
REARRANGEMENT OF CYCLIC 9-MEMBERS Si-PEROXIDES
R.A. Pototskiy1, R.A. Novikov2, A.O. Terentev1, G.I. Nikishin1, A.V. Arzumanyan1
1 - N. D. Zelinsky Institute of Organic Chemistry, Laboratory for Studies of Homolytic Reactions,
Moscow, Russia
2 - N. D. Zelinsky Institute of Organic Chemistry, Laboratory of Carbene Chemistry and SmallSized Cyclic Compounds, Moscow, Russia
Among organic peroxides, compounds with SiOO moiety are less known than their carbon
analogues. As the result there are few examples of reaction of silicon containing peroxides in
literature.
In the previous works we reported about successful synthesis of different silicon containing cyclic
peroxides [1,2].
Now we focused on investigation of treatment of such compounds with different reducers and
Lewis acids (LA).
It has been shown that treatment of the cyclic Si-peroxides with different
Si
Si
reducers leads to contraction of peroxide cycle on two oxygen atoms. Notably
O
O
each peroxide group lost one oxygen atom giving earlier unknown silylO
O
protecting diols. Reaction was carried out in diethyl ether medium at ambient
R
R'
temperature in the presence of 3-fold access of a reducer. The best results were
reached with triphenylphosphine. Yield of products were 60 to 75%, depending
on structure of starting substance. Such products may be used as building blocks
bin different bioactive compounds.
Treatment of bis-sililperoxides under LA action was studied. The reaction was carried out in
different reaction media with 2-fold excess of LA (SnCl4, TiCl4, AlCl3). It has been established that
the way of reaction depends on nature LA catalyst. For example, formation of lactones yield of 80 –
95% was observed (Bayer-Villiger-like reaction) in the presence of SnCl4. In case of TiCl4 the
combination of a regrouping and formation of an appropriate ketone was observed; with AlCl3
reaction did not flow past.
Summary, in this work chemical reactions of cyclic Si-peroxide compounds have been investigated.
Organic silicon peroxide compounds can enter various reactions leading to formation of lactones,
diols with a trialkylsilyl group, depending on reaction conditions that point to their high synthetic
potential.
References:
[1] Arzumanyan A.V., Terent’ev A.O., Nikishin G.I. et.al. Organometallics, 2014, 33, 2230-2246.
[2] Platonov M.M., Terent’ev A.O., Nikishin G.I. et.al. J. Org. Chem., 2008, 73, 3169-3174.
238
P128
EFFICIENT ONE-POT SYNTHESIS OF DIVERSE BENZO[C[CHROMENE6-ONES BY BASE-PROMOTED CASCADE REACTIONS
T.N. Poudel, Y.R. Lee
School of Chemical Engineering, Yeungnam University, Gyeongsan 712-749, Republic of Korea
Molecules bearing benzo[c]chromen-6-one and its derivatives are extensively distributed in nature.1
Some of these molecules exhibit biologically and pharmacologically important antitumor and
antibiotic activities,2 promote endothelial cell proliferation, and inhibit oestrogene receptor growth
activities.3 Due to the importance of these biological and pharmacological activities, several
synthetic methods have been devised to produce benzo[c]chromen-6-one derivatives. Of these
methods, the most useful method involves a Suzuki-Miyaura cross-coupling reaction followed by
metal or Lewis acid mediated lactonization of ester and methoxy groups.4 Recently, a new reaction
involving a microwave-assisted Diels-Alder reaction betwee 4-cyanocoumarin and 1-oxygenated
dienes followed by elimination and aromatization with a strong base was also described. 5 However,
these synthetic approaches included two-step reactions and required purification of the intermediate.
In addition, the starting materials used for these transformations were synthesized from
corresponding materials in two or more steps. Thus, a mild, general, and efficient one-pot synthetic
route for benzo[c]chromen-6-one derivatives using inexpensive catalysts and reagents is still in
demand, especially a route that allows minimization of the steps and access to diverse products.
We present herein a novel one-pot synthesis of a variety of benzo[c]chromen-6-one derivatives
using Cs2CO3-promoted reactions of substituted 2-hydroxychalcones and β-ketoesters. These
reactions involved cascade Michael addition/ intramolecular aldol/ oxidative aromatization/
lactonization and provided an efficient synthetic route for the production of biologically interesting
novel benzo[c]chromen-6-one molecules bearing several different substituents on benzene rings. As
an application of this methodology, several synthesized benzo[c]chromen-6-ones were transformed
into highly functionalized novel terphenyls.
References:
1. (a) Ya. L. Garazd, A. S. Ogorodniichuk, M. M. Garazd andV. P. Khilya, Chem. Nat. Compd.,
2002, 38, 424; (b) K. Ishiguro, M. Yamaki, M. Kashihara, S. Takagi and K. Isoi,
Phytochemistry,1990, 29, 1010; (c) H. Abe, K. Nishioka, S. Takeda, M. Arai, Y. Takeuchi and
T. Harayama, Tetrahedron Lett.,2005,46, 3197.
2. (a) T. Hosoya, E. Takashiro, T. Matsumoto and K. Suzuki, J. Am. Chem. Soc.,1994, 116,
1004;(b) C. A. James and V. Snieckus, Tetrahedron Lett.,1997, 38, 8149.
3. (a) J. M. Schmidt, G. B. Tremblay, M. Page, J. Mercure, M. Feher, R. Dunn-Dufault, M. G. Peter
and P. R. Redden, J. Med. Chem., 2003, 46, 1289;(b) J. Pandey, A. K. Jha and K. Hajela,
Bioorg. Med. Chem.,2004, 12, 2239.
4. (a) Q. J. Zhou, K. Worm and R. E. Dolle, J. Org. Chem.,2004, 69, 5147; (b) G. J. Kemperman,
B. Ter Horst, D. Van de Goor, T. Roeters, J. Bergwerff, R. Van der Eem and J. Basten,Eur. J.
Org. Chem.,2006, 14, 3169
5. M. E.Jung and D. A. Allen, Org. Lett., 2009, 11, 757.
239
P129
PRACTICAL SYNTHESIS OF 1,2,4-THIADIAZOLES VIA`
COPPER-MEDIATED HOMO-COUPLING OF THIOAMIDES
Y.-D. Sun, C.-R. Qi, H.-F. Jiang
South China University of Technology, College of Chemistry & Chemical Engineering, Guangzhou,
P. R. China
Thiadiazoles are regarded as an important class of five-membered heterocycles for many bioactive
molecules. One general method for the preparation of 1,2,4-thiadiazoles containing the same groups
in 3- and 5-positions was oxidative dimerization of the corresponding thioamides using oxidizing
agents. One the other hand, the transition metal-mediated oxidative transformations to construct
heterocycles have attracted great interest over the past decade. In particular, copper salts have been
successfully applied in the formation of C-hetero or hetero-hetero bonds, which exhibit great
potential for the construction of various heterocycles. On the basis of our recent developed Cucatalyzed method for synthesis of heterocycles1-5 and increasing interest of oxidative cross-coupling
reactions of two nucleophiles, herein, we disclose a novel method for 3,5-disubstituted 1,2,4thiadiazoles via copper(II)-mediated homo-coupling of thioamides involving C-N and N-S bond
formations (Scheme 1).
Scheme 1. Synthesis of 1,2,4-thiadiazoles
References
1. Huang, L.; Jiang, H.; Qi, C.; Liu, X. J. Am. Chem. Soc. 2010, 132, 17652.
2. Li, X.; Huang, L.; Chen, H.; Wu, W.; Huang, H.; Jiang, H. Chem. Sci. 2012, 3, 3463.
3. Gao, Y.; Yin, M.; Wu, W.; Huang, H.; Jiang, H. Adv. Synth. Catal. 2013, 355, 2263.
4. Zeng, W.; Wu, W.; Jiang, H.; Huang, L.; Sun, Y.; Chen, Z.; Li, X.; Chem. Commun. 2013, 49,
6611.
5. Sun, Y., Jiang, H.; Wu, W.; Zeng, W.; Wu, X. Org. Lett. 2013, 15, 1598.
240
P130
HIGHLY EFFICIENT SYNTHESIS OF TERTIARY α-HYDROXY KETONES
VIA CO2-PROMOTED REGIOSELECTIVE HYDRATION OF
PROPARGYLIC ALCOHOLS
H.-T. He, C.-R. Qi, H.-F. Jiang
South China University of Technology, College of Chemistry & Chemical Engineering, Guangzhou,
P. R. China
-Hydroxy ketones have attracted tremendous interest in biologically active natural product
research and synthetic chemistry. However, few of methodologies could be applicable for efficient
hydration of propargylic alcohols to form -hydroxy ketones except the Kucherov reaction using
mercury(II) salts as catalysts. A wide range of transition metals including Pd, Pt, Fe, Au, Ag, Ir and
Ru have been investigated for the hydration of alkynes, however, these catalytic systems either
showed low activity or led to side reactions such as Meyer-Schuster and Rupe rearrangements.
Therefore, the development of novel processes for the hydration of propargylic alcohols to produce
-hydroxy ketones with high efficiency is highly desirable.
Using CO2 as the feedstock, a great deal of work in many different fields, has been undertaken to
produce cyclic carbonates. In our previous work1, 2, we found that secondary amine was able to
attack the carbonyl group of the α-methylene cyclic carbonate to give the ring-opening product.
Recently, we set out to study whether water was capable to proceed the nucleophilic attack instead
of the secondary amines to furnish useful -hydroxy ketone derivatives (Scheme 1).
Scheme 1
References
[1] Qi C.; Jiang, H. Green Chem., 2007, 9, 1284.
[2] Qi C.; Huang, L.; Jiang, H. Synthesis, 2010, 9, 1433.
241
P131
UNEXPECTED DIRECT CONVERSION OF FUSED 1,2,5SELENADIAZOLES INTO 1,2,5-THIADIAZOLES
L.S. Konstantinova, E.A. Knyazeva, O.A. Rakitin
N.D. Zelinsky Institute of Organic Chemistry RAS
Fused 1,2,5-thiadiazoles have attracted much attention because of their interesting chemical
properties and various possibilities for use as antibacterial and antiviral agents, agrochemicals and
as π-type building blocks for organic electronics, particularly for both low- and high-molecular
organic light-emitting diodes (OLEDs).1 Recently 1,2,5-thiadiazole derivatives were recognized as
efficient electron acceptors and successfully used in the preparation of radical-anion salts revealing
antiferromagnetic exchange interactions in their spin systems and conductive charge-transfer
complexes.2 Although methods for the preparation of fused 1,2,5-thiadiazoles are numerous and
well elaborated, there is still a lack of syntheses of derivatives containing electron-deficient
heterocycles.
We have found that treatment of 1,2,5-selenadiazoles fused with nitrogen heterocycles, such as
piperazine and thia(selena)diazole with S2Cl2 in DMF gave unexpectedly corresponding 1,2,5thiadiazoles in high yields. This is the first case of direct substitution of the selenium to sulfur atom
in 1,2,5-selenadiazoles. The driving force of this reaction is the precipitation of elemental selenium
which was isolated from the reaction mixtures in practically quantitative yield.
We gratefully acknowledge financial support from the Russian Foundation for Basic Research
(Project 13-03-00072), from the Presidium of the Russian Academy of Sciences (Programme No. 8)
and from the Leverhulme Trust (Project IN-2012-094).
1. Todres Z.V., Chalcogenadiazoles: Chemistry and Applications, CRC Press/Taylor & Francis:
Boca Raton, 2012, 290 pp.
2. N. A. Semenov, N. A. Pushkarevsky, E. A. Suturina, E. A. Chulanova, N. V. Kuratieva, A. S.
Bogomyakov, I. G. Irtegova, N. V. Vasilieva, L. S. Konstantinova, N. P. Gritsan, O. A. Rakitin,
V. I. Ovcharenko, S. N. Konchenko, A. V. Zibarev Inorg. Chem., 2013, 52, 6654.
242
P132
ACTIVATION OF HYDROPEROXIDES BY TETRAALKYLAMMONIUM
BROMIDES
E.V. Raksha1, Yu.V. Berestneva1, N.A. Turovskij1, M.Yu Zubritskij2
1 - Donetsk National University, Physical chemistry Department, Donetsk, Ukraine
2 - L.M. Litvinenko Institute of Physical Organic and Coal Chemistry National Academy of
Sciences of Ukraine, Donetsk, Ukraine
The investigation of supramolecular catalysis of organic peroxides decomposition is the actual
direction in the development of peroxide initiators chemistry. There are a wide range of catalytic
systems for the radical decomposition of hydroperoxides and quaternary ammonium salts are
occupied an important place among of them. The key feature of supramolecular hydroperoxides
decomposition in the presence of Alk4NBr is the complex formation between the reactants [1].
Systematic kinetic investigations of the interaction between hydroperoxides and Alk4NBr have been
carried out [1]. Activation energies of the hydroperoxides thermolysis and catalytic decomposition
have shown to be change simbatically. Kinetic parameters of the hydroperoxide-catalyst complex
decomposition have been determined. Lowering of the activation barrier for the complex-bonded
hydroperoxide decomposition as compared with its thermolysis in acetonitrile is 40 kJ·mol-1.
The interaction of tert-butyl as well as 1,1,3-trimethyl-3-(4-methylphenyl)butyl hydroperoxides
with tetraalkylammonium bromides (Alk4NBr) has been studied by NMR spectroscopy. The
complexation between reactants was observed by relative change of the chemical shifts in the NMR
1
H spectra. The complex formation between the hydroperoxide molecule and corresponded
quaternary ammonium salt has been proved. Thermodynamic parameters of complex formation
have been determined.
The equilibrium constants of complex formation (KС) between tert-butyl hydroperoxide and
Alk4NBr have been determined both by NMR 1H and 13C spectroscopy. The values of the ΔcompH
for the hydroperoxide complex with investigated salts are negative and lie are within -20 ÷ -9
kJ·mol-1 7 in CDCl3 solution that corresponds to the formation of weak hydrogen bonds. Similar
effect has been observed in CD3CN solution for the hydroperoxide-Alk4NBr systems.
The equilibrium constant values as well as complexation enthalpies decrease with intrinsic
tetraalkylammonium cation volume increasing and this effect is observed over the temperature
range 297-313 K. Complexation enthalpies defined by kinetic and NMR spectroscopy methods
coincide.
The structural model has been proposed for the complex of hydroperoxides with Alk4NBr. It
includes the hydroperoxide molecule, salt cation and anion, as well as solvent molecule. Structural
reorganization of the hydroperoxide fragment is the key factor of the chemical hydroperoxide
activation in the presence of Alk4NBr.
[1] N.А. Тurovskij, E.V. Raksha, Yu.V. Berestneva, et al. in: Polymer Products and Chemical
Processes. Techniques, Analysis, and Applications, Editors: R.A. Pethrick, E.M. Pearce, G.E.
Zaikov. – Toronto, New Jersey: Apple Academic Press, 2013. – 323 p. – P. 269-284.
[2] N.А. Тurovskij, Yu.V. Berestneva, E.V. Raksha, et al. Polymers Research Journal. – 2014. –
Vol. 8, No. 2. – P. 85 – 90.
[3] N.А. Тurovskij, E.V. Raksha, Yu.V. Berestneva, M.Yu. Zubritskij. Russian Journal of General
Chemistry – 2014. – Vol. 84, Iss. 1. - P. 16-17.
[4] N.А. Тurovskij, Yu.V. Berestneva, E.V. Raksha, et al. Monatshefte für Chemie - Chemical
Monthly DOI 10.1007/s00706-014-1234-5.
243
P133
THE AZA-COPE-MANNICH REACTION: APPLICATION TO THE
SYNTHESIS OF UNNATURAL L-ALANINE DERIVATIVES
N.K. Ratmanova, D.S. Belov, I.A. Andreev, A.V. Kurkin
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
Unnatural amino acids represent a nearly infinite array of diverse structural elements for the
development of new leads in peptidic and non-peptidic compounds. Due to their seemingly
unlimited structural diversity and functional versatility, they are widely used as chiral building
blocks and molecular scaffolds in constructing combinatorial libraries.
Herein we report the synthesis of the enantiopure unnatural L-alanine derived transoctahydrocyclohepta[b]pyrroles 5a and 5b via the aza-Cope-Mannich reaction (Scheme 1). Epoxide
2 (the source of chirality) was prepared according to the literature procedures from commercially
available alcohol 1 applying Shi epoxidation protocol.1 The LiClO4-meditated epoxide ring-opening
of 2 with L-alanine ethyl ester gave the diastereomeric mixture of amino ethanols 3a and 3b. After
the chromatographic separation the compounds 3a and 3b were obtained as single isomers with
high enantiomeric purity (ee = 99% and 86% respectively, chiral HPLC). The hydrogenation of 3a
and 3b on the Lindlar catalyst gave desired alkenes 4a and 4b and unexpected side products (S)–
and (R)–ethyl 2–(4,5,6,7–tetrahydro–1H–indol–1–yl)propanoates. Finally, carrying out the azaCope-Mannich reaction under previously optimized conditions2 gave the target enantiopure
products 5a and 5b without epimerization.
Scheme 1. Synthesis of target compounds 5a and 5b.
As a result, two diastereomeric unnatural L-alanine analogues 5a and 5b were synthesized in 5
steps from commercially available materials. The study showed that conditions of the aza-CopeMannich reaction are mild enough to be applied in the complex settings, for example, to the
synthesis of molecules with several stereocenters which are prone to racemization.3
This study was supported by the Russian Foundation for Basic Research (RFBR), Russia (Projects
No. 14-03-31685, 14-03-31709, 14-03-01114).
References:
1. Wang, Z.-X.; Cao, G.-A.; Shi, Y. J. Org. Chem. 1999, 64, 7646–7650.
2. Belov, D. S.; Lukyanenko, E. R.; Kurkin, A. V.; Yurovskaya, M. A. J. Org. Chem. 2012, 77,
10125–10134.
3. Ratmanova, N. K.; Belov, D. C.; Andreev, I. A.; Kurkin, A. V. Tetrahedron: Asymmetry 2014,
25, 468–472.
244
P134
MECHANISTIC STUDIES OF PALLADIUM-MEDIATED ALKYNE
INSERTION REACTION USING ELECTROSPRAY IONIZATION TANDEM
MASS SPECTROMETRY
K.S. Rodygin1, L.L. Khemchyan2, V.P. Ananikov2
1 - Saint Petersburg State University, Institute of Chemistry, Stary Petergof, Russia
2 - N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Rapid development of transition metal catalysis allows rational design of a new methodology to
carry out three-component coupling. To achieve this aim challenging question concerning
mechanistic features of insertion reaction should be resolved.[1]
Oxidative addition of an aryl halide to Pd in Pd(PPh3)4 (a common source of Pd in cross-coupling
reactions) is the first step in the catalytic cycle. Addition of an alkyne to the mixture containing
Pd(PPh3)2ArX results in the formation of another intermediate, Pd(Ar)(PPh3)2(alkyne)X. The
intermediate containing the alkyne-unit has three possibilities to evolve: π-complex, acetylide or
vinyl complex (insertion product).
For development of the present project it was important to reveal the nature of transition metal
intermediates and their role in the catalytic cycle in order to improve selectivity and scope of
three-component coupling reaction. The questions of key importance in this regard (see Scheme):
how facile is the insertion reaction? And what types of complexes – π-complex, acetylide or vinyl
complex – are formed?
Few important features of the studied system deserve a note. Oxidative addition proceeds with
formation of Pd complex, the corresponded ion was detected as [Pd(PPh3)2Ph]+. The elimination of
PPh3-containing species is typical and expected under these conditions. More interesting series of
alkyne insertions into Pd-C bond starting from initial complex lead to the formation of
Pd-containing vinyl complexes. Reductive elimination results in formation of corresponded
substituted alkenes, dienes, triene and tetraene. Note, formation of these Pd-free olefinic species
provides an evidence for the fact of alkyne insertion into Pd-C bonds.
On the next stage ESI-(+MS/MS) experiment via collision-induced dissociation (CID) was
performed. The detected fragment ions serve as an additional evidence for the investigated alkyne
insertion step. In the present study we were able to distinguish π-complex and insertion intermediate
using ESI-(MS/MS) experiment.
K.R. gratefully acknowledges Saint Petersburg State University for a postdoctoral fellowship (№
12.50.1560.2013).
References
[1] Hydrofunctionalization, V.P.Ananikov, M.Tanaka (Eds.), Springer, 2013, Heidelberg. ISBN
978-3-642-33734-5.
245
P135
FACILE AND EFFICIENT SYNTHESIS 2-AMINO-4H-CHROMENES VIA
SOLVENT-FREE CASCADE ASSEMBLING OF SALICYLALDEHYDES
AND CYANOACETATES
F.V. Ryzhkov, R.F. Nasybullin, M.N. Elinson
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow,
Russian Federation
2-Amino-4H-chromenes (or 2-amino-4H-benzo[b]pyranes) are of particular interest as they belong
to privileged medicinal scaffolds serving for generation of small-molecule ligands with highly
pronounced spasmolitic-, diuretic-, anticoagulant-, and antianaphylactic activities [1]. The current
interest in 2-amino-4H-chromenes bearing nitrile functionality arises from their potential
application in the treatment of human inflammatory TNFα-mediated diseases, such as rheumatoid
and psoriatic arthritis, and in cancer therapy [2].
The development of solvent-free organic synthesis has become an important research area. This is
not only due to the need for the more efficient and less labour-intense methodologies for the
synthesis of organic compounds, but also because of the increasing importance of the
environmental considerations in chemistry. The elimination of volatile organic solvents in organic
synthesis is also the most important goal in ‘green chemistry’.
We were prompted to use a convenient and facile solvent-free cascade methodology for the
synthesis of 2-amino-4H-chromene scaffold from salicylaldehydes and cyanoacetates. We have
found that potassium fluoride as catalyst can produce, under solvent-free mild conditions, a fast and
selective cascade trasformation of salicylaldehydes and cyanoacatates into substituted at ambient
temperature 2-amino-4H-chromenes chromenes in 88–98% yields.
The catalytic procedure utilizes simple equipment; it is easily carried out and is valuable from the
viewpoint of environmentally benign diversity-oriented large-scale processes. This efficient
potassium fluoride catalyzed solvent-free approach to substituted 2-amino-4H-chromenes represents
a new synthetic concept for cascade reactions, and allows for the combination of the synthetic
virtues of conventional cascade processes with ecological benefits and convenience of solvent-free
procedure.
1. H. Aryapour, M. Mahdavi, S.R. Mohebbi, Frch. Pharm. Res., 2012, 35, 9, 1573-1582.
2. J. Skommer, D. Wlodkowic, M. Matto, M.Eray, J. Pelkonen, Leukemia Res., 2006, 30, 322-333.
246
P136
A NEW 3D CHEMICAL FORMULAS FOR ANALYZING OF
GEOMETRICAL STRUCTURES OF ACTIVE BIOMOLECULES IN
«STRUCTURE-ACTIVITY» PROBLEM
E.A. Smolenskii, A.N. Ryzhov, P.O. Guskov, I.V. Chuvaeva
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
We suggest a new way (“the method of triangles”) to describe 3D molecule structures and solid surfaces with
account their spatial geometry making the difference between stereo and conformational isomers. The new
formulas allow using well-known procedures of the “structure-property” and “structure-activity” problems for
large molecules. Furthermore, the method clears the novel ways of circumscribing solid surfaces and in
“structure-catalytic activity” problems. The approach is based on taking into account every of the spatialorientated atom triples i , j , k , designating triangle. Let us to consider vertex i of the triangle and vectors

V ij

Vi


V j , V ik

Vi

V k being the entries of the i-row of the Matrix of Geometrical Distances (MGD). And
now we proceed to description in terms of the triangles matrix:


ijk
:
i
j
k
1 
V ij
2
ijk

V jk
ijk

n ijk ;
ijk
1  
V ij V jk sin
2

; n ijk

V ij

V ij

V jk

V jk
.
Since a vectors product determines the triangle, it automatically means an orientation of the triangle surface in
space. There are 3 sets of indexes with the same direction of normal vectors n ijk and 3 ones in opposite. One can

selects internal or external triangles from the triangle matrix by following rule: triangle
m
i , j , k and
i, j, k :
n ijk V
is external, if
ijk
0 ; for triples of atoms placed on one line n ijk is determined as vector
m
that is perpendicular to and finished on this line and started from the mass center of molecule.

Changing internal triangles in the matrix
by zeros, we get the external triangles matrix
ijk
contains the same external triangle i , j , k

ex
ijk
. This matrix
three times. Thus, we define geometrical structure of a molecule.
Usually a biomolecule activity is defined by small site being complimentary to its natural substrates. The site (“kcomplex”) is consisted of k inter-oriented triangles. Vector F m of entry numbers a lm for every type of the kcomplex triangles in molecule with number m may be called as “3D chemical formula” of this molecule. One can
M
k
selects the triangles of k-complex considering the matrix ( M
CN
m
dimension) of entry numbers a lm for
m 1
every type of the k-complex triangles in each compound of the set Pm ( m
(1, M ) ) of active and non-active
M
substances. Here a lm ( m
1, M
, l
k
C N ) ) is the entry number of k-complex with number l in m -
(1,
m
m 1
compound, taking into account conformational isomerism, M – the number of compounds, N m - the number of
M
triangles in m-compound, N
N m - the general number of triangles in all substances. This matrix is based on
m 1
3D chemical formulas. Here we must using rule: any triangle being among type of triangles contained in inactive
substances cannot be contained in k-complex. Remaining triangles (approximately, they are contained in kcomplex; their number, as show on example of set of castanospermines tested by anti-HIV activity [G.W.J. Fleet
et al. FEBS Letters. 1988. V. 237. № 1-2. P. 128-132], as a rule, less than number of active compounds) is used
for making of additive scheme for calculating of biological activity.
So, 3D chemical formulas can be used for describing genes, catalyst surfaces, proteins and other biomolecules.
247
P137
A PROBLEM OF DEFINITION OF CHEMICAL EQUILIBRIUM IN
CONTEMPORARY CHEMISTRY
A.N. Ryzhov, E.A. Smolenskii, P.O. Guskov, M.S. Molchanova
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Unfortunately, a many definitions of chemical equilibrium of systems exist and are used now. In
process of our investigation, we find that principle of detailed equilibrium is sufficient but not
necessary condition of chemical equilibrium from the viewpoint of formal kinetics. We propose a
new definitions:
1.
Steady-state chemical system is called chemical system with constant temperature, pressure,
volume and activities of compounds.
2.
Equilibrium chemical system is called steady-state and adiabatically isolated system.
3.
System with detailed equilibrium is called equilibrium system with equilibrium in all
elementary reactions.
4.
Quasiequilibrium chemical system is open system with time of parameter stabilization been
more less than time of changing of external conditions.
Necessary and sufficient condition of chemical equilibrium is equality between sum of velocities of
elementary reactions with getting of some compound and sum of velocities of elementary reactions
with expenses of this compound for all compounds of system.
For system with three compounds
A
vBA
vAC
B
vAB
vCA
C
vBC
vCB
in the case of detailed equilibrium
(S=[A]+[B]+[C])
k
AC
k
CB
k
BA
k
AB
k
BC
k
CA
,
Sk
A
k
Sk
B
k
AB
k
CB
k
AB
BA
k
k
CB
CB
k
AB
k
BC
,
Sk
C
k
BC
k
AC
k
BC
CB
k
k
AC
AC
For this system in the common case of equilibrium
248
k
BC
k
CA
.
BA
k
CA
k
BA
AB
k
k
CA
CA
k
BA
k
AC
,
P138
SYNTHESIS, STRUCTURE AND THERMAL PROPERTIES OF
PROPYLENE OXIDE, CARBON DIOXIDE AND L-LACTIDE
TERPOLYMERS
Z.N. Nysenko1, E.E. Said-Galiev1, Ya.E. Belevtsev2, S.I. Daineko2, M.I. Buzin3, G.G. Nikiforova4,
A.M. Sakharov1
1 - N.D.Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Moscow,
Russia
2 - A.N.Nesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences,
Physical Chemistry, Moscow, Russia
3 - A.N.Nesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences,
Academy of sciences, Polymer Physics, Moscow, Russia
4 - A.N.Nesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences,
Polymer Physics, Moscow, Russia
Poly(propylene carbonate) (PPC) is a sustainable polymer that undergoes complete ash-free
incineration accompanied by the formation of CO2 and H2O. PPC is prepared by copolymerization
of propylene oxide (PO) with CO2 and it exhibits attractive physical and mechanical properties
responsible for its potential practical applications. It is known that ester units introduction into a
polymer chain promotes increasing its biodegradability.
Copolymers with different L-lactide concentrations were synthesized in the presence of zinc adipate
The combination of 1Н, 13С, and 2D {1Н-13С}HMBC NMR, DSC, FT-IR spectroscopy, and GPC
study results allows one to assume that copolymerization of СО2, PO and L-lactide yields to
partially crystalline terpolymers composed of propylene carbonate blocks combined with L-lactic
acid blocks and may be depicted by segment II of structure represented onto Scheme.
The synthesis of the terpolymers is not aggravated by side reactions. No inversion of the
configuration of L-lactide occurs during its addition to the polymer chain and the copolymer
possesses optic activity that depends on the L-lactide concentration in its chain. All possible types
of the PO addition (head-to-head, head-to-tail, and tail-to-tail), where head-to-tail addition
predominates, are found in the propylene carbonate blocks. L-Lactic acid content increase was
shown to be accompanied with elevation of terpolymers onset degradation temperature values.
The research was supported by the Russian Ministry of Education and Science (Contract No.
14.513.11.0139).
249
P139
SIMPLE PRECURSORS FOR THE REGIOSELECTIVE SYNTHESIS OF
METHYLENE-EXPANDED ANALOGUES OF C-NUCLEOSIDES
V.K. Brel1, A.V. Samet2, L.D. Konyushkin2, V.V. Semenov2
1 - A.N. Nesmeyanov Institute of Organoelement Compounds
2 - N. D. Zelinsky Institute of Organic Chemistry
Nucleosides with heterocyclic base linked to sugar through C–C bond instead of C–N attachment in
natural nucleosides attract much attention because of their chemical and enzymatic stability.
Compounds with methylene group inserted between the ring oxygen and the carbon atom linked to
the base moiety are considered as ring-expanded (six-membered ring) analogues of nucleosides
(Figure 1, A). Several of these molecules showed potent antiviral and antitumor activity.
F ig u re 1
We have developed the synthesis of C2 chiral derivatives of
dihydrolevoglucosenone 1a, 2a, and 3–7 as simple precursors for
preparation of methylene-expanded C-nucleosides (A), using pyrolysis of
cellulose as a key step followed by hydrogenation of LG and
introduction of vinyl and ethynyl fragments to 2-position.
6
O
5
Cellulose
stainless steel
autoclave
2% Pd/C (Sibunit)
1
O
6
2
4
HO
5
3
O
o
EtOAc, 40
4
3
2
O
O
20 bar, 8 h
DLG
LG
85%
O
HC
H2C
CMgBr
o
OH
O
R
3: Ph
C
A
O
1
O
Het
Et2O, rt, 2 h
THF, 40 , 2 h
+
RC
N
CMgBr
-
O
O
R
N
4: p-Me-Ph
5: p-F-Ph
o
54-75%
6: Ac
O
Et2O,
-40 , 3 h
1a CH
Cu(OAc)2
OH
O
OH
O
PhCH2N3
O
O
OH
O
63%
42%
2a
+
+
O
O
H2O, rt, 1 h
CH2
CH
N
N
N
84%
7
OH
OH
CH2Ph
CH2
O
O
1b
4.8%
3.8%
2b
The opening of 1,6-anhydrohexitols acetal ring could be used for transformation of derivatives 3–7
into methylene-expanded C-nucleosides (Figure 1, A).
250
P140
SYNTHESIS AND BIOLOGICAL EVALUATION OF
FURANOALLOCOLCHICINOIDS
E.S. Schegravina1, Yu.V. Voitovich1, N.S. Sitnikov1, V.I. Faerman1, V.V. Fokin1, H.-G. Schmalz2,
S. Combes3, D. Allegro4, P. Barbier4, I.P. Beletskaya5, E.V. Svirshchevskaya6, A.Yu. Fedorov1
1 - Department of Organic Chemistry, Nizhny Novgorod State University, Gagarina av. 23, Nizhny
Novgorod 603950, Russian Federation
2 - University of Cologne, Department of Chemistry, Koln, Germany
3 - Institut Paoli-Calmettes, Aix-Marseille Universite, Laboratory of Integrative Structural and
Chemical Biology, Marseille, France
4 - Aix-Marseille Universit, INSERM UMR_S 911, CRO2 F-13005, Marseille, France
5 - M.V.Lomonosov Moscow State University, Department of Chemistry, Moscow, Russian
Federation
6 - Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry RAS, Moscow, Russian Federation
A series of conformationally flexible furan-derived allocolchicinoids was prepared from
commercially available colchicine in good to excellent yields using a three-step reaction sequence1.
Compounds containing a hydroxyl group in the pseudo-benzylic position of the furan side chain
exhibited high cytotoxicity toward epithelial and lymphoid cell lines (AsPC-1, HEK293 and Jurkat)
in the nanomolar concentration range.
In vivo studies also demonstrated significant activity of compounds bearing a hydroxymethyl
fragment in the α-position of the furan ring against the tumor growth without symptoms of neurotoxicity.
Acknowledgment
We thank the Russian Foundation for Basic Research (projects 14-03-91342 and 12-03-00214-a),
The Ministry of Education and Science of The Russian Federation (project 4.619.2014/K). The
research is partly supported by the grant №02.В.49.21.0003 of The Ministry of Education and
Science of the Russian Federation to Lobachevsky State University of Nizhni Novgorod.
References
1. Voitovich, Yu.V., Sсhegravina, E.S., Sitnikov, N.S. Faerman, V.I., Fokin, V.V., Schmalz, H.-G.,
Comes, S., Allegro, D., Barbier, P., Beletskaya, I.P., Svirshchevskaya, E.V., Fedorov, A.Yu.
Synthesis and biological evaluation of furanoallocolchicinoids. J. Med. Chem. 2014 (submitted)
251
P141
TETRAMETHYLENECYCLOOCTANE – A BASIS FOR
POLYSPIROCYCLIC SMALL RING ARCHITECTURES
K.N. Sedenkova, E.B. Averina, S.G. Bakhtin, T.S. Kuznetsova, N.S. Zefirov
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
1,3,5,7-Tetrakis(methylidene)cyclooctane (1, TMCO) – a symmetric tetraene with highly reactive
exo-cyclic double bonds – represents a promising starting compound for the synthesis of
polyspirocyclic small ring structures, including rotanes and heterorotanes. Nevertheless, up to date
the synthesis of TMCO was mentioned in one short communication without an experimental
procedure [1]. We developed a straightforward synthesis of TMCO from commercial adamantane1,3-dicarboxylic acid (2). The key stage of the synthesis is fragmentation of adamantane pattern of
tetrabromide 3 under the treatment with zinc.
CH2Br
COOH
Zn, NaI, Na2CO3
4 steps
COOH
74%
Br
CH2Br
Br
2
DMF, 60%
1 (TMCO)
3
TMCO was shown to demonstrate high reactivity toward diazomethane, dihalocarbenes and
epoxidizing reagents, undergoing multiple cyclopropanations or epoxidations of four double bonds
to yield polyspirocyclic products 4–6.
X
X
[1+2]-cycloaddition
or epoxydation
X
1
X
4, X=CH2, 80%
5a, X=CCl2, 95%
5b, X=CBr2, 65%
5c, X=CBrF, 50%
6, X=O, 50%
Stereochemical features of polyspirocyclopropanated compounds 5,6 have been thoroughly
examined in experimental (NMR) and theoretical (DFT) studies. Comprehensive stereochemical
assignment of TMCO adducts with dihalocarbenes and polyspiroepoxy products was achieved.
In course of the work we have found that carrying out the fragmentation of adamantane derivative 3
in presence of traces of water leads to the formation of bis(methylidene)bicyclononane 7. The
addition of dihalocarbenes to diene 7 was shown to be stereoselective, giving solely the products of
exo-addition to double bonds 8a–c, that was by unambiguously proved by RSA for 8a.
CXY
3
CHX2Y, NaOHaq
Zn, NaI, Na2CO3
DMF/H2O, 160oC, 25%
CH3 TEBA, CH2Cl2
7
CH3
8a, X=Y=Cl, 87%
8b, X=Y=Br, 72%
8c, X=Br, Y=F, 43%
CXY
In conclusion, we elaborated a preparative gram-scale approach to TMCO and obtained a series of
unique polyspirocyclic structures starting from this highly reactive tetraene.
We thank the Russian Foundation for Basic Research (Projects 14-03-31989-mol_а, 14-03-00469a) and Presidium RAS (program №8P) for financial support of this work.
[1] Stepanov, F. N.; Sukhoverkhov, V. D.; Baklan, V. F.; Yurchenko, A. G. Zh. Org. Khim. 1970, 6,
884–885; J. Org. Chem. USSR (Engl. Transl.) 1970, 6, 278–284.
252
P142
USING HAuCl4 AS A SINGLE SOURCE OF METAL TO PRODUCE
SOLUBLE Au(Pr3)Cl COMPLEXES AND Au(0) PARTICLES
A.E. Sedykh1, S.S. Zalesskiy2, A.S. Kashin2, V.P. Ananikov2
1 - Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia; Higher
Chemical College, Russian Academy of Sciences, Moscow, Russia
2 - Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
A simple approach was developed for the synthesis of homogeneous and heterogeneous gold
catalysts. One of the most common gold compounds – HAuCl4 was used as a single source of
metal. Efficient one-pot synthesis procedure was created for preparation of gold complexes with
various phosphine or phosphite ligands Au(PR3)Cl (90 – 99% yield). The developed method gives
excellent results even for electron-deficient ligands and sterically hindered Buchwald-type
phosphines.
Various gold(0) nanoparticles were prepared using simple and available reductants. The
morphology of metal particles was studied and characterized with high-resolution field-emission
scanning electron microscopy (FE-SEM). It was found that the size and shape of the growing
particles can be controlled simply by selecting a reducing agent. Several unique types of structured
gold materials were prepared, such as particles arranged in a well-developed porous network,
hierarchical agglomerates and metal mirror composed of ultrafine particles.[1]
.
[1] Zalesskiy, S.S.; Sedykh, A.E.; Kashin, A.S.; Ananikov, V.P J. Am. Chem. Soc. 2013, 135, 3550.
253
P143
MOLECULAR INTERACTIONS AND EXTRACTION OF PEPTIDES IN
IONIC LIQUIDS SYSTEMS
M.M. Seitkalieva, V.V. Kachala, K.S. Egorova, V.P. Ananikov
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
In past decade, ionic liquids (ILs) have been weightiest matter because of their well-favored
properties for variety of physical, chemical and biological application. [1]
The technologies of ILs mediated extraction have shown the good prospects for replacing
traditional methods in separating natural bioactive homologues. They widely have been investigated
as extracting phases in liquid-liquid and aqueous two-phase systems for amino acids and proteins.
For peptides no such large achievement were reached and the mechanisms of peptide – IL
interactions remain to be established. Recently, we have studied interactions of imidazolium-based
ILs with peptides built from L-alanine and L-valine by NMR spectroscopy. [2] High sensitivity of
ILs to the nature of peptides and remarkably capability to distinguish a small change in the amino
acid sequence was demonstrated, that allowed further to study the molecular nature of the
separation process.
Hereinafter the back extraction of peptides in a two-phase ‘ionic liquid – organic solvent’ system
was performed and mechanism of peptide transition was studied.
The slice-selective NMR experiments were applying for effectively monitoring extraction process
that allowed discovering the molecular mechanism of peptide transition from the ionic liquid to
organic phase. The results suggested that the extraction occurred by molecular diffusion of
individual peptide molecules, which passed from IL to the organic solvent without structural
changes.
The selection of the extraction system was carried out, and imidazolium-based ILs: ethyl acetate petroleum ether system was used for effective partition of structurally similar peptides. Was
demonstrated that the extraction efficiency and selectivity increased with increasing the molecular
concentration of peptides. Obtained results have potential application in separation and analysis of
biomolecules.
[1] (a) V. P. Ananikov, Chem. Rev., 2011, 111, 418; (b) K. S. Egorova and V. P. Ananikov,
ChemSusChem, 2014, 7, 336.
[2] M. M. Seitkalieva, A. A. Grachev, K. S. Egorova and V. P. Ananikov, Tetrahedron, 2014,
10.1016/j.tet.2014.02.025s.
254
P144
SYNTHESIS AND BIOLOGICAL EVALUATION OF ANALOGS OF
NATURAL ANTIMITOTIC PRODUCTS USING
PARSLEY AND DILL SEED EXTRACTS
D.V. Tsyganov1, N.B. Chernysheva1, D.V. Demchuk1, A.V. Samet1, L.D. Konyushkin1, M.N.
Semenova2, V.V. Semenov1
1 - N. D. Zelinsky Institute of Organic Chemistry
2 - N. K. Kol’tsov Institute of Developmental Biology
Analogs of antimitotic natural products podophyllotoxin (PT) and combretastatin A-4 (CA4) as
well as plant-derived glaziovianin A were synthesized using allylpolyalkoxybenzenes from dill and
parsley seed oil. The targeted molecules were evaluated in vivo in a phenotypic sea urchin embryo
assay for antimitotic and microtubule destabilizing activity. Structure–activity relationship studies
identified CA4 analogs with 3,4,5-trimethoxyphenyl and 3,4-methylenedioxy-5-methoxyphenyl
ring A and 4-methoxyphenyl ring B as potent antiproliferative agents with high cytotoxicity against
a panel of 60 human cancer cell lines including multi-drug resistant cells. The most active aza- and
oxa-PTs featured myristicin-derived ring E. Cytotoxic effect of tested compounds was attributed to
microtubule destabilization resulted in cell cycle arrest followed by apoptotic cell death. The
effective threshold concentrations (EC) resulting in mitotic abnormalities in the sea urchin embryos
are presented in Figure.
Considering these encouraging data from phenotypic and mechanistic studies, some compounds
may prove to be lead candidates for further in vivo studies to assess its potential as an anti-tumor
agents.
255
P145
STRUCTURES OF CAPSULAR POLYSACCHARIDES OF NOSOCOMIAL
PATHOGEN ACINETOBACTER BAUMANNII AND THEIR CLEAVAGE
BY SPECIFIC BACTERIOPHAGE TAIL-SPIKE DEPOLYMERASES
A.S. Shashkov1, S.N. Senchenkova1, Y.A. Knirel1, M.M. Shneider2, K.A. Miroshnikov2, A.V.
Popova3, N.V. Volozhantsev3
1 - N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
2 - M.M. Shemyakin & Y.A. Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of
Sciences, Moscow, Russia
3 - State Research Center for Applied Microbiology and Biotechnology, Obolensk, Moscow Region,
Russia
Nosocomial infections due to multidrug-resistant pathogen Acinetobacter baumannii have become
increasingly common. Phage therapy is promising for their treatment. A prerequisite of
bacteriophage adsorption on the bacterial cell surface necessary for the infection and the following
lysis of the cell is the cleavage of the protecting bacterial capsular polysaccharide (CPS) by a
specific structural depolymerase (phage tail spike). To develop the biochemical basis for phage
therapy of A. baumannii infections we studied structures of the CPSs of these bacteria and
mechanisms of the CPS depolymerisation by bacteriophage tail spikes.
CPS structures of 5 strains of A. baumannii (28, 1053, 1432, 5075 and ACICU) were established
using chemical methods along with 1H и 13С NMR spectroscopy. Degradation of the CPSs from A.
baumannii 28 and 1053 was performed with recombinant tail-spike depolymerases of
bacteriophages Fri1 and AP22, respectively. Structures of the CPSs and degradation products were
established by 1H and 13C NMR spectroscopy and high-resolution ESI MS. FriI glycosidase
hydrolysed the CPS of strain 28 at one of the glycosidic linkage to give mainly a nonasaccharide
composed of three CPS repeats (Scheme 1). AP22 lyase cleaved the CPS of strain 1053 by
-elimination in a hexuronic acid residue to give unsaturated trisaccharide (major) and
hexasaccharide (minor) (Scheme 2).
Scheme 1. Depolymerisation of CPS of A. baumannii 28 by phage FriI tail-spike hydrolase.
QuiNAc4NAc, 2,4-diacetamido-2,4,6-trideoxy-D-glucose; n = 1 (major), 0, 2-4 (all minor).
Scheme 2. Depolymerisation of CPS of A. baumannii 1053 by phage AP22 tail-spike lyase.
4,5HexNAcA, 2-acetamido-2,4-dideoxy-L-erythro-hex-4-еnuronic acid.
256
P146
ON PHOTOLUMINESCENCE PROPERTIES OF INDIUM-EXCHANGED
ZSM-5 ZEOLITE
A.I. Serykh
Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences
Optical properties of indium-exchanged ZSM-5 zeolite with different indium content have been
studied. It has been found for the first time that reduced In-ZSM-5, containing low-valence In+
cations exhibits strong photoluminescence emission both in UV and visible light region. The
intensity of visibly light luminescence strongly increases with increase of indium content in InZSM-5. The emission spectrum of low-indium loaded In-ZSM-5 is represented mainly by an
intense UV band at 350 nm (Fig.1). The excitation spectrum consists of three irregularly-shaped
bands at about 220-230 nm, 260 nm and 308 nm. Lifetime measurements show that the UV
emission of this sample has a single component (approximately 5×10-3 ms). The emission spectrum
of In-ZSM-5 with high indium content (Fig. 2) is represented by two intense emission bands both in
UV and visible-light regions. The visible light emission decay is complex and has a fast (10-3 ms or
faster) and at least two slow components (0.05 ms and 0.2 ms). The excitation spectra of both UV
and visible-light emission bands are represented by three irregular shaped peaks at 220-230 nm, 260
nm and 308-314 nm. These peaks can be induced by the electronic excitations transitions similar to
those X 1Σ+(0+)C 1 (1), X 1Σ+(0+)B 3 1(1) and X 1Σ+(0+)A 3 0(0+) in indium halides or
1
S01P1, 1S03P2 and 1S03P1 transitions in indium-doped alkali halides (C, B and A transitions).
The emission in In-ZSM-5 occur due to irradiative transition from the lowest excited state (which is
a triplet state according to its lifetime) The UV luminescence most probably is associated with
isolated In+ cations, while the visible-light emission can be related to the formation of In+ oligomers
or clusters in the excited state.
Fig.1. Emission and excitation spectra of lowindium-loaded In-ZSM-5 (4 wt.% In) reduced in
hydrogen at 823 K and evacuated at the same
temperature for 2 h.
E m is s io n
308
350
260
In te n s ity /a .u .
223
229
E x c ita tio n
200
250
300
350
400
450
500
550
600
W a v e le n g th /n m
E x c ita tio n
308
223
Fig. 2. Emission and excitation spectra of highindium-loaded In-ZSM-5(9 wt. % In) reduced in
hydrogen at 823 K and evacuated at the same
temperature for 2 h.
E m is s io m
351
c
314
229
260
In te n s ity /a .u .
a
570 590
b
200
250
300
350
400
450
500
550
600
650
700
750
800
W a v e le n g th /n m
257
P147
CATALYTIC OXIDATION OF OLEFINS BY TBHP IN THE PRESENCE OF
TRANSITION METALS
M.Y. Sharipov, A.O. Terent’ev
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences 119991 Moscow,
Leninsky prospekt, 47, Russia
The transition metal catalyzed selective oxidation of organic compounds with the aim of organic
peroxides preparation is a demanded field of the oxidative processes chemistry. The publications of
recent years show that organic peroxides possess a high antimicrobial, antiparasitical and fungicidal
activity. It was discovered that cyclic diperoxides reveal a high antischistosomal activity
(IC50<15μM) [1].
The role of t-BuO• and t-BuOO• radicals in oxidative reactions of alkanes, alkenes and
alkylbenzenes with t-BuOOH was earlier showed by Minishi group; the processes were catalyzed
by Fe(III) or Mn(III) – porphyrins [2].
In this study the reaction conditions were found under which a selective oxidation of olefins by tertbutyl hydroperoxide gives vicinal bis-peroxides in the presence of transition metal complexes.
Proposed mechanism involves the stages of oxidation of metal complex by tert-butyl hydroperoxide
(a). Radical t-BuO• reacts with t-BuOOH in nonbasic solvent giving t-BuОO• radical (b), which
adds to substrate giving the corresponding radical (с); this latter one is then oxidized via a ligandtransfer process (d). Mn(III) salts transfer a peroxy-group to the carbon-centered radical, while
Mn(II) salts decompose t-BuOOH giving t-BuO• (e).
This work is supported by the Grant of the Russian Foundation for Basic Research (Grant 14-0300237-a) and the Grant of the Program of Supporting for Basic Research of the Presidium RAS.
1. K. Ingram, I.A. Yaremenko, I. Krylov, L. Hofer, A.O.Terent'ev, J.Keiser. J. Med. Chem., 2012,
55 (20), c. 8700–8711
2. F. Minisci, F. Fontana, S. Araneo, F. Recupero, S. Banfi and S. Quici. J. Am. Chem. Soc., 1995,
117 (1), c. 226–232
258
P148
ONE-POT TWO-STEP SYNTHESIS OF OPTICALLY ACTIVE 1-AMINO
PHOSPHONATES BY PALLADIUM-CATALYZED
HYDROGENATION/HYDROGENOLYSIS OF 1-(2-PHENYLHYDRAZONO)
PHOSPHONATES
I.A. Shergold, N.S. Goulioukina, I.P. Beletskaya
Lomonosov Moscow State University, Chemistry Department, Moscow, Russia
Heterogeneous palladium catalysts such as Pd/C or Lindlar catalyst are routine and the most
popular hydrogenation tool. Over the recent decade chiral palladium complexes of diphosphine
ligands have emerged as new efficient metal catalysts for homogeneous asymmetric reduction of
C=C, C=O, and especially C=C–N or C=N double bonds within a wide variety of prochiral
substrates.[1] Thus we have successfully employed this methodology for the preparation of
nonracemic 1-hydroxy[2] and N-hydroxy-1-amino phosphonates[3] starting from carbon-heteroatom
unsaturated precursors. Herein we present our preliminary results on the synthesis of optically
active 1-amino phosphonates (a well-known class of bioactive compounds[4]) by two-step procedure
taking advantages of both homogeneous and heterogeneous palladium catalysts.
In search of easy-to-use starting substrates we opted for 1-(2-phenylhydrazono) phosphonates 1
which were isolated as the single (Z)-isomers, the double bond geometry having been confirmed by
X-ray crystallographic analysis. We have shown that phosphonates 1 can be smoothly reduced by
hydrogen gas with Pd(OAc)2/(R)-Cl-MeO-BIPHEP as the catalyst and (1S)-(+)-10-camphorsulfonic
acid (CSA) as the activator to furnish corresponding 1-(2-phenylhydrazino) phosphonates 2 in high
yields and enantiomeric excess 90–94%. The subsequent hydrogenolysis of intermediate products 2
was performed in situ over 10% Pd/C without any loss of optical purity.
References:
1
a) Q.-A. Chen, Zh.-Sh. Ye, Y. Duan, Y.-G. Zhou. Chem. Soc. Rev. 2013, 42, 497–511; b) J.H. Xie, Sh.-F. Zhu, Q.-L. Zhou. Chem. Rev. 2011, 111, 1713–1760.
2
N.S. Goulioukina, G.N. Bondarenko, A.V. Bogdanov, K.N. Gavrilov, I.P. Beletskaya. Eur. J. Org.
Chem. 2009, 510–515.
3
N.S. Goulioukina, I.A. Shergold, G.N. Bondarenko, M.M. Ilyin, V.A. Davankov, I.P. Beletskaya.
Adv. Synth. Catal. 2012, 354, 2727–2733.
4
a) F. Orsini, G. Sello, M. Sisti. Curr. Med. Chem. 2010, 17, 264–289; b) P. Kafarski, B. Lejczak.
Posphorus, Sulfur, and Silicon 1991, 63, 193–215.
259
P149
CARBOHYDRATE-BASED PHOSPHINES AND THEIR SUPPORTED
PALLADIUM COMPLEXES: APPLICATION IN SUZUKI-MIYAURA AND
HECK REACTIONS
J. Shi1, Zh. Zhou2, H. Zheng1, Q. Zhang1
1 - College of Chemical Engineering, Guangdong University of Petrochemical Technology,
Maoming 525000, China
2 - College of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou,
341000, China
Several carbohydrate-based phosphines derived from glucose, (methyl 3-deoxy-4,6-Ophenylmethenyl-α-D-altropyranosido-3-)disubstituted-phosphine, and some of their palladium
complexes have been synthesized and fully characterized. The well defined palladium complexes
and those generated in situ are highly effective for Suzuki-Miyaura and Heck reactions. The oxygen
atoms in the carbohydrate unit were found to participate in catalytic cycle and contribute to catalytic
activity.
O
Ph
O
Ph
O
O
OMe
R2P
Pd
NMe2
Pd
2) NaOMe
NMe2
2
OMe
O
2
O
O
O
Cl
Ph
O
O
OMe
1) Pd(COD)Cl2
2) NaOMe
R2P
OH
1
R = Ph, Cy, But
O
R2P
Pd
R2P
O
O
Ph
OMe
O
O
3
This project was supported by the National Natural Science Foundation of China (No. 21272037),
the Natural Science Foundation of Fujian Province (2011J01033).
References:
1. Shi, J.-C.; Zhou, Z.; Zheng, S.; Zhang, Q.; Jia, L.; Lin, J. Tetrahedron Lett. 2014, 55, 2904.
2. Zheng, S.; Jia, L.; Liu, Z.; Jiang, D. Huang, Y.; Nong, L.; Zhang, Q.; Shi, J.-C. Chin. J. Org.
Chem. 2014, 34, DOI: 10.6023/cjoc201404034.
3. Shi, J.-C.; Kang, B.-S.; Mak, T. C. W. J. Chem. Soc., Dalton Trans. 1997, 2171.
260
P150
A NEW SYNTHETIC APPROACH TO 3-PHOSPHORYLATED PYRAZOLES
E.D. Shinkarev, N.N. Makukhin, N.S. Goulioukina, I.P. Beletskaya
Moscow State University, Department of Chemistry, Moscow, Russia
Phosphorylated pyrazoles[1] represent intriguing structural motives for the design of biologically
and pharmaceutically active compounds and are a subject of growing interest in different fields such
as agrochemical and medicinal chemistry. Besides the biological properties, pyrazolyl phosphonates
received considerable attention as efficient coordinating ligands and as precursors to N-heterocyclic
carbenes (NHC). In spite of great potentialities for the practical usage, synthetic approaches to
phosphorylated pyrazoles are few in number and often involve multistep reaction sequences. So the
search of novel efficient methods for pyrazolyl phosphonates preparation remains an actual task.
Recently we have shown that 1,3-dipolar cycloaddition reaction of aryldiazomethanes with
dimethyl 1-formamidovinylphosphonate (1) affords 5-substituted dimethyl 3-formamido-4,5dihydro-3H-pyrazol-3-ylphosphonates (2) or thermodynamically more stable isomeric 3-substituted
dimethyl
5-formamido-4,5-dihydro-1H-pyrazol-5-ylphosphonates
(3).
The
subsequent
aromatization of 2 or 3 with formamide elimination and formation of 3-phosphorylated pyrazoles 4
have been performed under acidic conditions.[2]
In continuation of this work, we have elaborated a simple one-pot procedure for the direct
preparation of ring substituted phosphonates 4. It was found that the cycloaddition of
aryldiazomethanes onto phosphonate 1 smoothly proceeds in methanol or ethanol in the presence of
catalytic amounts of K2CO3 at room temperature to furnish 3-phosphorylated pyrazoles 4 in good to
excellent yields. The methodology is compatible with various functional groups and provides a
broad scope of ring substituted (5-aryl-1H-pyrazol-3-yl)phosphonates. The structure features of the
products obtained will be also discussed.
[1] T. E. Ali, S. M. Abdel-Kariem, Heterocycles, 2012, 85, 2073-2109.
[2] N. S. Goulioukina, N. N. Makukhin, I. P. Beletskaya, Tetrahedron, 2011, 67, 9535-9540.
261
P151
SYNTHESIS OF CHIRAL ISOCYANIDES BASED ON β-AMINO ACIDS
FOR MULTICOMPONENT REACTIONS
O.I. Shmatova, D.P. Zarezin, V.G. Nenajdenko
Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992, Russia
It is known that peptides possess a high biological activity and could affect on different
physiological processes (regulation of hormonal activity, digestion, appetite, pain, higher nervous
activity, arterial pressure etc.). But the biggest drawback of peptide as therapeutic drug is its low
metabolic stability. Various structural modifications of α-amino acids are using to improve stability
of biological active peptides. One of the possible modifications of α-amino acid is its
homologization and replacement for β-amino acid in peptide chain.
On the other hand, isonitriles is actively used in Ugi and Passerini multicomponent reaction for
preparing peptides and depsipeptides. We decided to develop synthesis of new chiral isonitriles
based on β-amino acids and investigated its use in multicomponent reaction for obtaining
peptidomimetics containing fragment of β-amino acid.
Isonitriles 4 were synthesized from commercial available N-formyl-α-amino acids 1 by ArndtEistert reaction (preparing diazaketone 2 and subsequent Wolf rearrangement in the presence of
nucleophile – alcohols, amines or amino acids). Then isonitriles 4 were synthesized from obtained
derivatives 3 by treatment POCl3/Et3N.
HOOC
1
1) ClCOOEt
R
NHCHO 2) CH2N2
O
N2
PhCOOAg
R
2
NHCHO
NuH
O
R
3 Nu
NHCHO
POCl3
O
Et3N,
CH2Cl2
4 Nu
R
NC
R = Ph, Me, Bn, iBu, iPr, secBu, CH2Indolyl;
MeOOC R''''
NuH = R'OH, R''R'''NH,
.
NH2
New chiral isonitriles 4 participate in the Ugi reaction to give the corresponding di-, tri- or even
tetrapeptide 5 in good yields. Moreover these isonitriles 4 react smoothly with carboxylic acids and
ketones/aldehydes affording depsipeptides 6.
O
4 Nu
R
NC
R2NH2
+
R1
O
R3
R1COOH
R4
R2
N HN
O R3
R
O
R4 O
Nu
5
O
O
4 Nu
R
NC
R3
R1
R4
R
O
+
O R3
R1COOH
262
HN
R4 O
O
Nu
6
P152
MULTICOMPONENT REACTION OF 3-HYDROXYCHROMONE WITH
ALDEHYDES AND THE MELDRUM`S ACID
S.V. Shorunov, B.V. Lichitsky, A.O. Osipov, A.N. Komogorttsev, A.A. Dudinov, M.M.
Krayushkin
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
3-Hydroxychromones possess considerable interest due to their unique optical properties 1-2. Thus
the chemical synthesis of the derivatives of 3-hydroxychromone is of prime interest. The
convenient method of the synthesis of those compounds is the multicomponent reaction (MCR)
which allows one to synthesize the broad set of the derivatives of the 3-hydroxychromones in one
stage. In the present work we explored the multicomponent condensation of 3-hydroxychromone
(1) with aldehydes (2) and the Meldrum`s acid (3). The condensation was carried out by refluxing
the methanolic solution of the reactants for 2 hours with triethylamine employed as the base. It was
demonstrated that the main products of such a reaction are esters (4). We assume that the
condensation proceeds via the initial formation of the arylmethylene derivatives of the Meldrum`s
acid with subsequent addition of the 3-hydroxychromone which leads to the unstable cyclic
intermediates (5). Probably after formation the lactones (5) undergo the ring opening by action of
methanol and triethylamine forming the final products (4).
Thus we elaborated a convenient general approach to chromone esters (4) based on the
multicomponent condensation of 3-hydroxychromone (1) with aldehydes (2) and Meldrum`s acid
(3).
References:
1. Chevalier K, Grun A, Stamm A, Schmitt Y, Gerhards M, Diller R. J. Phys. Chem., 2013, 117,
11233.
2. Das R, Duportail G, Ghose A, Richert L, Klymchenko A, Chakraborty S, Yesilevskyy S, Mely
Y.Phys.Chem.Chem.Phys, 2014, 16, 776.
263
P153
NOVEL CHIRAL FLUORINE-BASED PROBES FOR MONITORING OF
ASYMMETRIC REACTIONS BY NMR SPECTROSCOPY
S.A. Shyshkanov, N.V. Orlov, V.P. Ananikov
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russian
Federation
Development of chiral molecular sensors for analysis of chiral compounds has got great attention
during past decade [1]. Their main advantage over traditional chiral auxiliary reagents are both
short sample preparation and analysis time allowing quick analysis of huge amounts of samples. To
date enantioselective fluorescent sensors are widely used for analysis of chirality, however, NMR
sensors can be equally efficient to meet these needs.
In the present study we have investigated the efficiency of 19F NMR spectroscopy, which combines
high sensitivity and wide NMR scale range of fluorine nucleus, for the quantitative analysis of
chiral carboxylic acids. For this purpose fluorine-based chiral probes were synthesized starting from
cheap and available R-2-amino-1-butanol (scheme 1).
Scheme 1.
The derivatization protocol developed during previous investigations [2, 3] was found to be
efficient for analysis of carboxylic acids, containing a stereocenter in α-or β-position, directly in
NMR tube without isolation and purification of the resulting diastereomers (scheme 2).
Scheme 2.
The obtained results demonstrated the efficiency of 19F NMR spectroscopy for quick and accurate
analysis of chiral carboxylic acids. The best results were obtained using a derivative containing 2fluoro-substituted phenyl ring, which is apparently due to the ultimate contribution of the steric and
electronic effects.
The design criteria of the chiral probes, scope and limitations of the protocol and implementation to
NMR monitoring of enantiomeric excess of asymmetric reactions will be covered in the poster.
Acknowledgements
The research was supported by the Russian Foundation for Basic Research (project 12-03-01094).
References
1. L. Pu, Acc. Chem. Res. 2012, 45, 150.
2. N. V. Orlov, V. P. Ananikov, Chem. Commun. 2010, 46, 3212.
3. N. V. Orlov, V. P. Ananikov, Green Chem. 2011, 13, 1735.
264
P154
SYNTHESIS OF PYRIDINE FROM ALDEHYDE, ALKYNE AND
AMMONIUM ACETATE THROUGH RHODIUM(III) CATALYZED NANNULATION REACTION
Y.-K. Sim, C.-H. Jun
Yonsei University, Department of Chemistry, Seoul, Korea
Transition metal catalyzed C-H bond activation is one of powerful tools to generate valuable
carbon-carbon bond in organic synthesis. Especially, Rh(III) catalyzed heterocyclic N-annulation
has attracted great attention due to its numerous important applications and facile preparation of
isoquinoline derivatives.1 Despite of development of many synthetic methods for isoquinoline
synthesis, only a few pyridine synthetic method have been reported. In the course of our studies on
Rh(I) catalyzed hydroacylation,2 we found a new synthetic method for pyridine synthesis which
employs Rh(I) hydroacylation and subsequent Rh(III) catalyzed pyridine synthesis from the
resulting , -unsaturated ketone, ammonia, alkyne and Cu(II) as oxidizing reagent. This new
protocol allows to prepare multifunctional pyridine derivatives.3
1. Song, G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, 3651-3678.
2. Jun, C.-H.; Lee, H.; Hong, J.-B.; Kwon, B.-I. Angew. Chem., Int. Ed., 2002, 41, 2146-2147.
3. Sim, Y.-K.; Lee, H.; Park, J.-W.; Kim, D.-S.; Jun, C.-H. Chem. Commun., 2012, 48, 1178711789.
265
P155
AMINOIMINOPHOSPHORANATE ARENE RUTHENIUM COMPLEXES:
SYNTHESIS, STRUCTURE AND СATALYSIS
Y.S. Sinopalnikova, T.A. Peganova, N.V. Belkova, A.M. Kalsin
A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Moscow,
Russian Federation
Aminoiminophosphoranate (NPN) ruthenium complexes are scarcely explored organometallic
compounds. New 18ē (1) and 16ē (2) arene ruthenium complexes with various N- and Psubstituents at the NPN ligands were synthesized by reaction of the sodium
aminoiminophosphoranates with dimeric arene ruthenium chlorides. The zwitter-ionic NPN ligand
[1] is a strong σ, -donor, it can efficiently stabilize coordinatively unsaturated 16ē NPN complexes
and render them as stable as their 18ē precursors.
The neutral 18ē complexes 1 reversibly dissociate in solution to give cationic 16ē complexes 2, in
polar solvents the equilibrium is strongly shifted to the right side. The activation barriers ( G ) for
the dissociation process were estimated by EXSY and VT NMR; the equilibrium parameters ( G,
H, S) were found by UV-vis measurements in a wide range of temperatures (190-300 K).
The formally electron deficient 16ē complexes 2 can interact with 2ē donor ligands (MeCN, Py,
CO) to produce 18ē cationic complexes 3, although the acetonitrile and pyridine adducts are stable
only at low temperatures. These reactions were studied by NMR and UV spectroscopy in a wide
range of temperatures (190-300 K) to find their thermodynamic parameters. The cationic COcomplex is stable at ambient conditions due to the strong -acceptor ability of this ligand. It was
fully characterized by NMR and the structure was determined by X-ray analysis.
The complexes 1 and 2 were tested in model catalytic transfer hydrogenation of acetophenone in
isopropanol. Interestingly, the 18ē complexes are an order of magnitude more active than their 16ē
counterparts having non-coordinating anions (PF6-, BF4-, BArF4-). The activity is strongly enhanced
when more electron-releasing groups (alkyls) at N- and P- are used. The tentative mechanism is
proposed.
The authors thank the Russian foundation for basic research (grant RFBR 14-03-00345) for
financial support.
[1] Peganova, T.A.; Valyaeva, A.V.; Kalsin, A.M.; Petrovskii, P.V.; Borissova, A.O.; Lyssenko,
K.A.; Ustynyuk, N.A. Organometallics 2009, 28, 3021.
266
P156
COMPARISON OF PARTICLE SIZE EFFECT IN CH4 OXIDATION OVER
Pt VS Pd CATALYSTS
A.M. Batkin1, N.S. Teleguina1, G.O. Bragina1, A.K. Khudorozhkov2, V.I. Bukhtiyarov2,
A.Yu. Stakheev1
1 - Zelinsky Institiute of Organic Chemistry, Catalysis division, Moscow, Russia
2 - Boreskov Institute of Catalysis, SB RAS, Novosibirsk, Russia
Catalytic combustion of methane is a promising automotive exhaust gas after-treatment technology.
Supported noble metals (e.g. Pt and Pd) have been reported as active catalysts for methane
oxidation reaction and are preferentially used in automotive converters in spite of their high cost.
One of the most important factors influencing the efficiency of noble metal catalyst is the size of
metal particles. High metal dispersion increases the fraction of atoms accessible for a reaction. On
the other hand, turnover rates of oxidation reactions may depend significantly on the size of metal
particles (particle size effect). As a result, overall activity of the catalyst becomes a function of
metal dispersion (fraction of exposed atoms) and the particle size effect, and careful management of
metal particle size is required for achieving optimal performance and/or minimization of noble
metal loading.
In the present study we compared particle size effect in CH4 oxidation process over Pt/Al2O3 and
Pd/Al2O3. Catalytic tests were complemented by in-situ XPS study of the oxidation state of Pt and
Pd particles under reaction conditions for revealing a nature of the observed catalytic effects.
Catalytic studies demonstrated different dependencies of TOF on metal particle size for Pd and Pt
catalysts. Particle size effect for Pd catalysts is significantly pronounced: TOF increases by more
than order of magnitude with increase in d Pd from 1 to 22 nm. Therefore, the most favorable
performance is observed for the catalyst with Pt particle size ~ 4 nm. For Pt catalysts TOF increases
only by ~ 2-3 times with increasing particle size from 1 to 3-4 nm, and remains essentially constant
when d Pt exceeds 4 nm. As a result, the sample with maximal Pt dispersion (d Pt = 1.2 nm)
demonstrates the best overall activity in CH4 oxidation among Pt catalysts.
Results of in-situ XPS studies indicate that Pd particles remain in oxidized state in the course of the
reaction within the whole range of particle sizes (1 – 22 nm). On the other hand, for Pt catalysts
with bigger metal particles, XPS data showed that Pt remains mainly in the metallic state.
These data suggest that the observed dependence of the catalytic activity on metal particle size may
be associated with the change of the reaction pathway from Mars–van Krevelen mechanism for Pd
catalysts to Langmuir–Hinshelwood kinetics for Pt samples.
Acknowledgement: Financial support by RFBR grant # 12-03-01104-a is gratefully acknowledged
267
P157
SELECTIVITY CONTROL IN SEMIHYDROGENATION OF SUBSTITUTED
ALKYNES BY Pd PARTICLE SIZE
P.V. Markov1, O.V. Turova1, I.S. Mashkovsky1, A.K. Khudorozhkov2, V.I. Bukhtiyarov2,
A.Yu. Stakheev1
1 - Zelinsky Institiute of Organic Chemistry, Catalysis division, Moscow, Russia
2 - Boreskov Institute of Catalysis, SB RAS, Novosibirsk, Russia
Alkynes are versatile reagents in organic synthesis since C≡C group can be easily transformed to a
cis-alkene through stereoselective addition of hydrogen molecule. This so-called
semihydrogenation is often an important step in industrial processes as well as in laboratory-scale
reactions. However, careful control of stereoselectivity and minimization of over-hydrogenation is
required.
In this work we studied a relationship between the size of Pd nanoparticles (ranging from 1.5 to 22
nm) in 1%Pd/Al2O3 catalyst and the activity/selectivity in liquid-phase diphenylacetylene (DPA)
hydrogenation. The data obtained reveal a significant increase in turnover frequency (calculated per
surface Pd atom) and pronounced improvement of the in the catalyst selectivity with the increase in
Pd particle size (Fig. 1, (a) and (b) respectively).
The observed relationship can be explained by a strong adsorption of bulky alkyne and alkene
molecules on low-coordinated surface atoms of small Pd nanoparticles. Strong absorption reduces
TOF due to competition between adsorbed DPA molecules and hydrogen. Moreover, strong
adsorption of the intermediate alkenes impedes their desorption and favors secondary stage of
hydrogenation. On the other hand, when Pd particles grow in size, the percentage of lowcoordinated palladium surface atoms rapidly decreases. This improves turnover frequency and
enhances selectivity of the process.
16.0
96%
(a)
Selectivity in alkene
14.0
12.0
TOF, s-1
10.0
8.0
6.0
4.0
(b)
94%
92%
90%
88%
86%
2.0
0.0
84%
0
5
10
15
20
25
Pd particle size, nm
0
5
10
15
20
25
Pd particle size, nm
Fig. 1. Effect of Pd particle size on TOF [n(DPA)/n(Pdsurf)*s-1] (a) and selectivity toward stilbene
formation (b) in the course of DPA hydrogenation over 1%Pd/Al2O3.
Acknowledgement: Financial support by RFBR grant #13-03-12176 is gratefully acknowledged
268
P158
NOVEL CATALYST FOR SELECTIVE HYDROGENATION OF
ACETYLENIC BOND BASED ON PD NANOPARTICLES ENCAPSULATED
IN METAL-ORGANIC FRAMEWORK (NH2)-MIL-53(AL)
V.I. Isaeva, P.V. Markov, O.V. Turova, I.S. Mashkovsky, G.K. Kapustin, L.M. Kustov,
A.Yu. Stakheev
Zelinsky Institiute of Organic Chemistry, Catalysis division, Moscow, Russia
Selective semihydrogenation of an acetylenic function is a demanding task. Not only does the
stereoselectivity (E/Z ratio) need to be controlled, but the hydrogenation of the resulting olefin to
alkane must be suppressed as well. During the last decade the metal-organic framewoks (MOFs)
received a considerable attention as metal carriers for heterogeneous catalysis, which enable fine
tuning both activity and selectivity of the resulted heterogeneous systems. In this study we explored
catalytic performance the novel catalyst on the basis of Pd nanoparticles encapsulated in
microporous metal-organic frameworks MIL-53(Al) and NH2-MIL-53(Al) in liquid-phase
hydrogenation of diphenylacetylene (DPA) as the model substrate:
H2
Ph
Ph
P h (c is )
Ph
H2
Ph
Ph
Ph
P h (tra n s )
The important task of this research was the elucidation of an impact of the metal-organic framework
texture and the functional groups (NH2-) in organic linker on the catalytic performance of
enacapsulated Pd NPs composites.
Main results The catalysts demonstrate high activity and excellent selectivity in DPA
semihydrogentaion (Table 1). Selectivity toward alkene (diphenylethene - DPE) formation exceeds
90% at dipehylacetylene conversion as high as 95%. The catalysts also show high stereoselectivity
(E/Z ratio) toward formation of cis-isomer ( > 97%) and favorable stability.
Table 1. TONs and selectivity parameters in DPA hydrogenation
PH2 = 5 bar, Treact = 25oC, [DPA]/Pd ~ 4000
Catalyst
Solvent
ТОNDFA, s-1 ТОNDFE, s-1 rDFA/rDFE SDFE*
1%Pd/MIL-53(Al)
2.55
0.38
6.7
n-C6H14
1%Pd/NH2-MIL1.10
0.21
5.2
53(Al)
1%Pd/MIL-53(Al)
1.39
0.35
4.0
91.2%
CH3OH
1%Pd/NH2-MIL0.27
0.10
2.7
91.4%
53(Al)
* selectivity to alkene and cis-isomer was measured DPA conversion ~ 95%
Scis/(cis+trans)*
97.8%
98.3%
The data obtained imply that Pd/MIL-53(Al) nanocomposites can be considered as a promising
candidate for development of highly effective catalysts for liquid-phase selective bond
hydrogenation of C≡C bond.
Acknowledgement: Financial support by RFBR grant #13-03-12176 is gratefully acknowledged
269
P159
KINETIC RESOLUTION OF RACEMIC GERANYLCYCLOHEXYLACETIC
ACID TO ENANTIOMERS
S.G. Zlotin, G.V. Kryshtal, G.M. Zhdankina, A.A. Sukhanova, A.S. Kucherenko, B.B. Smirnov,
V.A. Tartakovsky
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospekt, 47,
119991 Moscow, Russia
Geranylcyclohexylacetic acid 1 is the active substance of Cygerole® that had manufactured in
Russia and used for curing of wounds, in particular surgery wounds, radiation or trophic ulcers and
burns. Furthermore, isoprenoid acids turned to be promising as tracking drugs for cell therapy of
various human diseases and injuries of vital organs and tissues with mesenchymal stem cell (MSC)
and MSC-derived cardiomyoblasts [1].
Acid 1 incorporates a stereocenter, however just racemic form of 1 is known so far. In order resolve
compound 1 to enantiomers we have applied a kinetic resolution method assuming that the
enantiomers would react with optically pure alcohols with different rates. (S)- and (R)-BINOLs
bearing a bulky C2-symmetric binaphthyl fragment have been chosen as the chiral auxiliaries. We
have shown that esterification of rac-1 with (S)-BINOL in the presence of DCC – DMAP afforded
compound 2a in 75% yield and with diastereomeric ratio of 90:10. Accordingly, the
diastereoselective reaction of rac-1 with (R)-BINOL gave ester 2b as the major product (dr 87:13).
Subsequent LiOH-promoted re-esterification of BINOL esters 2a or 2b with MeOH followed by a
basic hydrolysis of corresponding methyl esters 3a or 3b furnished optically enriched acids 1a or 1b
(80% or 75% ee, HPLC data) [2].
The presence of the long-chained geranyl group in compound rac-1 appeared a key
stereocontrolling factor that is crucial for a successful kinetic resolution of rac-1 to enantiomers 1a
and 1b. An analog of compound rac-1 bearing the prenyl group instead of the geranyl unit at the
stereogenic carbon atom generated with (S)-BINOL corresponding (S)-BINOL ester with poor
diastereoselectivity (dr 60:40).
References
1. B.B. Smirnov, G.V. Kryshtal, A.G. Konopljannikov, S.G. Zlotin, G.M. Zhdankina, RF Pat.
2301667, Chem. Abstr., 2007, 147, 110262.
2. S.G. Zlotin, G.V. Kryshtal, G.M. Zhdankina, A.A. Sukhanova, A.S. Kucherenko, B.B. Smirnov,
V.A. Tartakovsky, Mendeleev Commun., 2014, ahead a print.
270
P160
SYNTHESIS AND MASS-SPECTRA OF OLIGOSACCHARIDE
FRAGMENTS OF THE CAPSULAR POLYSACCHARIDE OF
STREPTOCOCCUS PNEUMONIA TYPE 3 AND THEIR
NEOGLYCOCONJUGATES WITH BSA
E.V. Sukhova1, D.V. Yashynsky1, Y.E. Tsvetkov1, E.A. Kurbatova2, N.E. Nifantiev1
1 - Laboratory of Glycoconjugate Chemistry, N. D. Zelinsky Institute of Organic Chemistry,
Russian Academy of Sciences, 119991 Moscow, Leninsky Prospect 47
2 - Mechnikov Research Institute of Vaccines and Sera, Russian Academy of Medical Sciences,
105064 Moscow, Malyi Kazennyi per. 5a
Pneumococcal infection is a leading cause of death throughout the world [1] and a major cause of
pneumonia, bacteremia, meningitis, and otitis media [2]. In the framework of a project directed to
the design of a pneumococcal conjugated vaccine based on synthetic carbohydrate ligands, 3aminopropyl glycosides of disaccharide fragments of the capsular polysaccharide of Streptococcus
pneumonia type 3 have been synthesized.
Neoglycoconjugates of the synthesized oligosaccharides with bovine serum albumin (BSA) have
been prepared by the squarate procedure. In the MALDI-TOF mass-spectrum, a wide peak was
observed with maximum at m/z 75733, which corresponds to inclusion into the conjugate of 19
disaccharide residues on average.
The obtained results can be used for development of synthetic and semisynthetic pneumococcal
polysaccharide vaccines and vaccines against various social diseases caused by encapsulated
bacteria.
References
1. O’Brien, K. L., Wolfson, L. J., Watt, J. P., Henkle, E., Deloria-Knoll, M., McCall, N., Lee, E.,
Mulholland, K., Levine, O. S., and Cherian, T. (2009) Lancet, 374, 893-902.
2. Weinberger, D. M., Harboe, Z. B., Sanders, E. A., Ndiritu, M., Klugman, K. P., Ruckinger, S.,
Dagan, R., Adegbola, R., Cutts, F., Johnson, H. L., O’Brien, K. L., Scott, J. A., and Lipsitch, M.
(2010) Clin. Infect. Dis., 51, 692-699.
This work was supported by the Russian Foundation for Basic Research, project No.14-03-00532A
271
P161
SYNTHESIS OF OLIGOSACCHARIDE FRAGMENTS OF THE CAPSULAR
POLYSACCHARIDE OF STREPTOCOCCUS PNEUMONIA TYPE 14 AND
THEIR NEOGLYCOCONJUGATES WITH BSA
E.V. Sukhova1, D.V. Yashynsky1, Y.E. Tsvetkov1, E.A. Kurbatova2, N.E. Nifantiev1
1 - Laboratory of Glycoconjugate Chemistry, N. D. Zelinsky Institute of Organic Chemistry,
Russian Academy of Sciences, 119991 Moscow, Leninsky Prospect 47
2 - Mechnikov Research Institute of Vaccines and Sera, Russian Academy of Medical Sciences,
105064 Moscow, Malyi Kazennyi per. 5a
Bacteria of the Streptococcus pneumoniae species are causative agents of severe inflammatory
diseases of the respiratory tract, meningitis, otitis, bacteremia, etc.[1-3] that sometimes have lethal
outcome[4]. In the framework of a project directed to the design of a pneumococcal conjugated
vaccine based on synthetic carbohydrate ligands, 2-aminoethyl glycosides of tetra-, hexa- and
octasaccharide fragments of the capsular polysaccharide of Streptococcus pneumonia type 14 have
been synthesized.
Neoglycoconjugates of the synthesized oligosaccharides with bovine serum albumin BSA have
been prepared by the squarate procedure. In the MALDI-TOF mass-spectrum, a wide peak was
observed with maximum at m/z 84342, which corresponds to inclusion into the conjugate of 18
hexasaccharide residues on average.
The conjugate of the synthetic hexasaccharide with BSA was shown to possess of high antigenic
activity comparable whit that for natural antigens of Streptococcus pneumonia type 14. This
compound has demonstrated significant protective effect in experiments with mice infected by vital
bacterial culture.
Diagnostic pneumococcal test systems based on the pneumococcus synthetic capsular
polysaccharide or on its fragments can be useful for avoiding shortcomings of natural
polysaccharides, such as presence of admixtures, using living cultures of microorganisms,
expensive methods of isolation and purification of antigens, and will result in creation of
qualitatively new modern ELISA test systems.
The findings can be used for development of synthetic and semisynthetic vaccines against
pneumococcus and other socially important microorganisms possessing a polysaccharide capsule.
References
1. Tatochenko, V. K. (2008) Zh. Detsk. Infekts., 2, 13-17.
2. Tatochenko, V. K. (2010) Zh. Mikrobiol., 5, 90-98.
3. Vishnyakova, L. A. (1993) Pulmonologiya, 3, 17-20.
4. O’Brien, K. L., Wolfson, L. J., Watt, J. P., Henkle, E., Deloria-Knoll, M., McCall, N., Lee, E.,
Mulholland, K., Levine, O. S., and Cherian, T. (2009) Lancet, 374, 893-902.
This work was supported by the Russian Foundation for Basic Research, project No.14-03-00532A
272
P162
ONE-POT SYNTHESIS OF TRIAZOLOQUINAZOLINONES VIA COPPER
CATALYZED TANDEM CLICK AND INTRAMOLECULAR C-H
AMIDATION
Ch.-M. Sun
Department of Applied Chemistry, National Chiao-Tung University, Hsinchu 300, TAIWAN
A novel and highly efficient copper catalyzed tandem synthesis of triazolo quinazolinones is
explored. The synthetic strategy involves a sequential one-pot click reaction followed by aerobic
intramolecular C-H amidation. Two distinct important transformations were carried out in one-pot
by employing a single cost effective copper catalyst. The milder, rapid, oxidant and ligand free
reaction conditions as well as broader substrate scope are the salient features of this novel protocol.
273
P163
PHARMACEUTICAL CO-CRYSTALS OF DIFLUNISAL AND
DICLOFENAC WITH THEOPHYLLINE
A.O. Surov, G.L. Perlovich
G.A. Krestov Institute of Solution Chemistry RAS, 153045, Ivanovo, Russia
The development of pharmaceutical co-crystals is one of the hot topics in the field of crystal
engineering nowadays as co-crystals can fine tune relevant physicochemical properties of active
pharmaceutical ingredients (API). In this work, we report new co-crystals of nonsteroidal antiinflammatory drugs diflunisal (DIF) and diclofenac (DIC) with theophylline (THP) (Figure 1).
According to the Biopharmaceutics Classification System (BCS), DIF and DIC belong to class II
drugs with low solubility and high permeability as most NSAIDs. Therefore, novel pharmaceutical
co-crystals for DIF and DIC with enhanced physicochemical properties are still highly interesting.
The co-crystals are characterized by single-crystal X-ray diffraction, differential scanning
calorimetry (DSC) and solution calorimetry. In addition, analysis of crystal lattice energies of the
co-crystals was done using PIXEL approach. Pharmaceutically relevant properties such as aqueous
dissolution, intrinsic dissolution rate and relative humidity stability are also reported.
In each structure, the asymmetric unit contains API and THP
molecules connected by almost linear O–H···N hydrogen bonds
involving the carboxylic acid of the API and an unsaturated N
atom of the imidazole ring of THP (acid-imidazole heterosynthon)
In addition, the API forms the C-H···O contacts with the
neighbouring THP molecule. The THP molecules are connected to
each other by N–H···O hydrogen bonds to form centrosymmetric
dimers that may be described in graph set notation as R 22 (10 ) .
Figure 1.
Therefore, both co-crystals have a similar organization of
intermolecular hydrogen bonds to form a four-component supramolecular unit which consists of a
THP centrosymmetric dimer and two APIs molecules. CSD survey and literature analyses show that
analogous hydrogen bonded systems are quite common in THP co-crystals. PIXEL calculations
reveal that crystal lattice energy of [DIC+THP] is higher than the one of [DIF+THP] on account of
increased dispersion energy between the DIC molecules.
The co-crystal formation enthalpies calculated from solution calorimetry experiments are small. It
suggests that energies of hydrogen bonds in the co-crystals and pure components are comparable,
and the packing energy gain is obtained mainly from weak van der Waals forces.
The intrinsic dissolution studies (IDR) show that [DIF+THP] IDR is comparable to that of pure
DIF. In case of [DIC+THP], the co-crystal form dissolution rate is found to be ca.1.3 times higher
compared to the initial API. The aqueous dissolution profile of [DIF+THP] demonstrates a classical
“spring and parachute” shape. For the [DIF+THP] co-crystal, a 5 hour time period corresponds to
the “spring” phase. This is followed by a longer-term “parachute” phase, when slow crystallization
and precipitation of the unstable DIF species occurs. The latter process lasts the following 25 hours.
In case of [DIC+THP] system, the “spring” effect is not so evident. After 5-6 hours of dissolution,
the concentration of [DIC+THP] co-crystal shows ca. 1.6 times the solubility of pure.
Relative humidity experiments were conducted in order to compare the RH storage stability of the
co-crystals to that of anhydrous theophylline. In contrast to THP, both co-crystals were stable at
100% RH. Further observations up to 2 months at 100% RH did not show any destruction or
transformations of the co-crystals.
This work was supported by a Grant from the President. МК- 67.2014.3 and RFBR (№ 14-03-31001).
274
P164
SYNTHESIS AND OLFACTORY PROPERTIES OF UNNATURAL
DERIVATIVES OF LILAC ALDEHYDES
P. Siska1, P. Fodran2, P. Szolcsanyi1
1 - Slovak University of Technology, Department of Organic Chemistry, Bratislava, Slovakia
2 - Slovak University of Technology, Department of Nutrition and Food Assesment, Bratislava,
Slovakia
Lilac aldehydes1 1 (Fig. 1) are naturally occurring monocyclic tetrahydrofuranyl terpenes
considered as principal olfactory molecules of lilac flowers (Syringa vulgaris). We have designed,
prepared and evaluated two sets of their unnatural racemic analogues as pure diastereomers. While
the synthesis of gem-dimethyl homologues 2–7 starts from geranyl acetate, the preparation of
methylene derivatives 8–10 commences from linalyl acetate. The key Lewis and/or Brønsted acid
catalysed cyclisation furnishes easily separable cis-/trans-tetrahydrofuranyl esters as common
advanced intermediates. The following functional group transformations lead to target aldehydes,
alcohols, nitriles and olefins (Fig. 1).
R
R = H or Me
geranyl acetate
R
O
O
FG = CO2Me, CH2OH
or
FG CHO, CN, CH=CH
CHO
linalyl acetate
2
(2-10)
(1)
(Figure 1)
The olfactory analysis revealed that while C-2 dimethylated homologues 2–7 exhibit similar herbal
scents, the corresponding C-2 demethylated derivatives 8–10 possesses a broader range of scents
with woody and/or flowery odours as dominant (Fig. 2). Unlike with homologues 2–7, the nature of
C-1 substituent and/or relative stereochemistry has significant effect on the scent variations within
the group of analogues 8–10. Finally, our results suggest that both installation and removal of
methyl group at C-2 significantly alters the olfactory properties of such unnatural derivatives 2–10
in comparison to their parent structures 1.
O
O
CHO
(10)
woody
vs.
O
CHO
vs.
(1)
flowery
(Figure 2)
[1] Wakayama, S.; Namba, S. Bull.: Chem. Soc. Japan 1974, 47, 1293.
275
CHO
(2)
camphoraceous,
minty, eucalypty
P165
DEVELOPMENT OF REGIOSELECTIVE REDUCTIVE
TRANSFORMATION OF 4,11-DIMETHOXY-5,10-DIOXO-2METHYLANTHRA[2,3-B]FURAN-3-CARBOXYLIC ACID DERIVATIVES
A.S. Tikhomirov1, O.A. Omelchuk2, A.E. Shchekotikhin1, M.N. Preobrazhenskaya1
1 - Gause Institute of New Antibiotics RASM, Moscow, Russia
2 - Mendeleyev University of Chemical Technology of Russia,Moscow, Russia
Previously, a series of linear furanoanthraquinones (anthra[2,3-b]furan-5,10-diones) was revealed as
potent topoisomerase I poisons capable of inhibiting the growth of tumor cells including lines with
activated mechanisms of multidrug resistance1. However, for further structure-activity relation
studies in a series of anthra[2,3-b]furan-5,10-diones the development of methodologies useful for
the diversification at position 3 of this scaffold is necessary. In the present work, we have
developed a new method of transformation of ethyl 4,11-dimethoxy-5,10-dioxo-2methylanthra[2,3-b]furan-3-carboxylate2 based on a selective reduction of carboethoxy group.
Generally a direct reduction of carboethoxy group can be performed with strong reductive agents
(LiAlH4, NaBH4, BH3-THF, etc.), but the presence of quinone moiety in ester 1 is limiting the
application of these reagents. Therefore we choose a strategy for reduction of anthrafurandione-3carboxylic acid derivatives via the corresponding chloroanhydride with mild reductive agents3,4. As
the first step, ethyl anthrafurandion-3-carboxylate 1 was transformed into chloroanhydride 2 by the
basic hydrolysis and subsequent treatment with SOCl2 in refluxing benzene. Reduction of
chloroanhydride 2 with diisobutylaluminium hydride (DIBAL-H) leads to the 3-hydroxymethyl4,11-dimethoxy-2-methylanthra[2,3-b]furan-5,10-dione (3) in low (5%) yield due to side the
reduction of the quinone moiety.
The unacceptable result encourages us for finding a more regioselective method of reduction of the
chlorocarbonyl group in anthrafurandione 2. Hydrogenation of chloroanhydride 2 using Pd/BaSO4
or Pd/C as the catalyst in toluene gives 4,11-dimethoxy-2-methylanthra[2,3-b]furan-5,10-dione-3carbaldehyde (4) in acceptable yield (57%). Reaction of anthra[2,3-b]furan-5,10-dione-3carbaldehyde 4 with NaBH4 in THF produces a high yield of the desired anthra[2,3-b]furan-5,10dione-3-carbinol 3. The structures of the new anthra[2,3-b]furan-5,10-diones 2-4 were confirmed by
methods of NMR and high resolution mass-spectroscopy methods.
1. Shchekotikhin, A. E.; Glazunova, V. A.; Dezhenkova. Eur. J. Med. Chem. 2011, 46, 423.
2. Tikhomirov, A. S.; Shchekotikhin, A. E.Chem. Heterocycl. Compd. 2014, 50, 271.
3. Seyden-Penne, J, Reductions by the Alumino- and Borohydrides in Organic Synthesis, 2nd
edition, Wiley-VCH, 1997, P. 99.
4. Bai, N.; Sha, Y.; Meng, G., Molecules, 2008, 13, 943.
276
P166
STUDY OF MECHANISMS OF DI-, OLIGO- AND POLYMERIZATION
REACTIONS OF ALKENES BY SYSTEMS BASED ON PHOSPHINE AND
α-DIIMINE NICKEL COMPLEXES
Yu.Yu. Titova1, L.B. Belykh2, F.K. Schmidt2
1 - Irkutsk State University, Institute of Oil and Coal-Chemical Synthesis, Irkutsk, Russia
2 - Irkutsk State University, Chemical Department, Irkutsk, Russia
Catalysis of lower alkenes (C2-C4) dimerization by nickel complexes is the subject of great number
of research for over four decades. At the present time there are several points of the nature view of
the catalytically active site in the process of di-, oligo-and polymerization of lower alkenes. The
most experimental justified concept is based on the decisive contribution to the catalytic process of
hydride complexes Ni (II), formed by the interaction of nickel (II) with an organoaluminum
compound are the most experimentally validated [1]. On the other hand, there are other points of
view, is not always justified experimentally.
Here, we report the results of study of the interaction mechanism between compounds of catalytic
systems based on phosphine and α-diimine complex of Ni(0), Ni(I) and Ni(II), with general
formulas Ni(PPh3)2(C2H4), Ni(PPh3)nCl (n = 2, 3), NiBr2(DAD-iPr or –CH3), Ni(DAD-iPr or –
CH3)2 (DAD(-iPr) = 1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene, DAD(CH3) = 1,4-bis(2,6-dimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene), with Lewis acids
(AlEt3, AlEt2Cl, AlEtCl2, B(F5C6)3, BF3·OEt2), the role of alkenes in the formation of catalytically
active species, and catalytic properties of these systems in a di-, oligo- and polymerization reactions
of lower alkenes.
During the study characteristics of the individual catalytic nickel complexes and systems based on
this complexes in combination with Lewis acids were determined in the process of oligomerization
of ethylene. For systems based on phosphine complexes of Ni(0) and Ni(I) by physical and
chemical methods of research (NMR-, EPR-, IR-spectroscopy) it was determined, that Ni(II)
complexes with an active Ni–C bond produced by interaction of starting components initiate
dimerization and oligomerization via the hydride mechanism.
Investigation of the interaction between components of systems based on α-diimine complexes of
Ni(0) and Ni(II) by EPR spectroscopy establish the existence of equilibrium between the complexes
Ni(I)[DAD(-iPr)], Ni+[DAD(-iPr)]- and the radical-anion bound to Al- or B-atoms [2]. In the
presence of substrate, this equilibrium shifts to the side of the radical-anion. Moreover, the part of
radical-anion associated with aluminum or boron is increases when the acidic properties of Al- and
B-containing co-catalysts are weakening. The EPR monitoring of α-diimine systems based on Ni(0)
and Ni(I) complexes proves that direct relationship between the activity in the polymerization of
ethylene and concentration of paramagnetic particles is absent. Perhaps, paramagnetic particles of
Ni(I) play the same function in the regeneration of Ni(II) active alkyl complexes, as in modified
phosphines systems [3].
This work was supported by Russian Foundation for Basic Research (№ 14-03-32037 mol_а) and a base
part of Government Assignment for Scientific Research from the Ministry of Education and Science, Russia
(№2014/51,project code:627). Authors gratefully acknowledge Irkutsk Supercomputer Center of the Russian
Academy of Sciences http://hpc.icc.ru.
[1] Shmidt, F.K., Kataliz kompleksami metallov pervogo perekhodnogo ryada reaktsii gidrirovaniya i dimerizatsii
(Hydrogenation and Dimerization Catalyzed by Complexes of First Row Transition Metals), Irkutsk: Irkutsk. Gos.
Univ., 1986. [2] Actual problems of magnetic resonance and its application: Abstracts of XVII International Youth
Scientific School. – Kazan: 2014. – P.136. [3] Yu.Yu. Titova, L.B. Belykh, A.V. Rokhin, O.V. Soroka, F.K. Schmidt,
Kinet. Catal., 55 (2014) 37-50.
277
P167
XAS (XANES & EXAFS) FOR CHARACTERIZATION OF METALORGANIC FRAMEWORKS
O.P. Tkachenko1, V.I. Isaeva1, E.V. Belyaeva1, W. Grunert2, L.M. Kustov1
1 - IOC RAS, Lab.14, Moscow, Russia
2 - RUB, Lehrstuhl fur Technische Chemie, Bochum, Germany
Recently, an approach, which incorporates functional “cartridge molecules” that are non-covalently
bound within MOFs has been demonstrated [1]. The goal of the present work is the purposeful
design of the composite materials comprising analogs of Zn-MOF-5 and Pd as advanced catalytic
systems. The palladium was introduced via impregnation or CVD methods. Transmission Zn K and
Pd K X-ray absorption spectra were measured at the Hasylab X1 station (DESY, Germany) using a
Si(111) double crystal monochromator. The spectra were recorded at 77 K in vacuum. Reference
spectra were taken using standard reference compounds: ZnO, Zn-foil, PdO and Pd-foil. Data
analysis was performed with the software package VIPER [2]. The required scattering amplitudes
and phase shifts were calculated by the ab initio FEFF8.10 code [3]. The fitting was done in the kand r-spaces.
The Zn K-edge XANES evidenced that zinc exists as Zn2+ ions in all synthesized organic
frameworks. Introduction of Pd has no impact on the Zn K XANES of MOFs. From the literature
[4] the shortest Zn-Zn distance in two nearest Zn4O units of MOFs-5 is ~ 3.78 Ǻ. The fitting results
of Zn K EXAFS gives the real distance between two Zn atoms in our samples is ~3.20 Ǻ, which
allows supposing the presence in our samples of some Zn species and/or MOF frameworks
interpenetrating each other like that observed in [5]. The introduction of Pd in samples results in the
increase of the amount of interweaved cells.
The Pd K-edge XANES evidenced that palladium exists in metallic state. The fitting results of Pd K
EXAFS has shown that the stabilization of very small Pd nanoparticles could be achieved using the
micro- and mesoporous metal organic frameworks as the host matrices. In some cases the bimodal
distribution of Pd was observed. Both the preparation method and palladium precursor impact to Pd
particles size.
The activity of metal organic frameworks contained Pd was investigated in the liquid-phase
hydrogenation catalytic reactions [6-9].
References
[1] Z. Wang, S. M. Cohen, Chem. Soc. Rev. 38 (2009) 1315.
[2] K.V. Klementiev, www.cells.es/Beamlines/CLAESS/software/viper.html.
[3] A.L. Ankudinov, B. Ravel, J.J. Rehr and S.D. Conradson, Phys. Rev. B, 58 (1998) 7565.
[4] R-Q. Zou, R-Q Zhong, M. Du, T. Kiyobayashi, Q. Xu, Chem. Commun., 2467 (2007).
[5] Havicovic, M. Bjorgen, U. Olsbye, et al. J. Am. Chem. Soc. 129 (2007)3612.
[6] V.I. Isaeva, O.P. Tkachenko, I.V. Mishin, E.V. Afonina, G. I. Kapustin, L.M. Kozlova,
W.Grunert, L.M. Kustov, Studies in Surface Science and Catalysis, 175 (2010) 707.
[7] V.I. Isaeva, A.L. Tarasov, O.P. Tkachenko, G.I. Kapustin, I.V. Mishin, C.E. Solov’eva, L.M.
Kustov, Kinetics and Catalysis 52 (2011) 94.
[8] V.I. Isaeva, O.P. Tkachenko, E.V. Afonina, L.M. Kozlova, G.I. Kapustin, W.Grünert, S.E.
Solov’eva, I.S. Antipin, L.M. Kustov, Microporous and Mesoporous Materials, 166 (2013) 167.
[9] E.V. Belyaeva, V.I. Isaeva, E.E. Said-Galiev, O.P. Tkachenko, S.V. Savilov, A.V. Egorov, L.M.
Kozlova, V.Z. Sharf, L.M. Kustov, Russ. Chem. Bull. 2 (2014) 396.
278
P168
COMPARISON OF s, d AND f-ELEMENTS COMPLEXATION ABILITY
WITH PENDANT PHOSPHORYLATED AZACROWN ETHER
G.S. Tsebrikova1, V.E. Baulin1, I.N. Polyakova2, I.S. Ivanova2, E.N. Pyatova2, A.Yu. Tsivadze1
1 - Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow, Russia
2 - Kurnakov Institute of General and Inorganic Chemistry, Moscow, Russia
New ligands searching for selective binding of biologically active metal cations and radionuclides is
a quite actual problem. Appending different phosphoryl containing substituents to the azacrown
molecules is a promising approach to the new effective chelators design.
New complexes of N,N′-bis(diphenylphosphorylmethyl)-4,13-diazaO
O
18-crown-6 (L) [ML](ClO4)2, where М2+ = Zn, Cu, Co and Ni, are
P h 2 (O )P
N
N
P (O )P h 2
synthesized. Its composition is confirmed by elemental analyses and
IR-spectroscopy data. The crystal structure of L and [CuL](ClO4)2 is
O
O
determined by X-ray diffraction.
L
As a result of copper complex formation the macrocycle conformation changes. Two nitrogen
atoms in the free ligand deviate from the average oxygen atoms plane to the one side, and in the
copper complex – to the different sides. The copper atom has surrounding in the shape of
asymmetrically prolated tetragonal bipyramide [2N+2О(Р)]+2O. Comparison of the structure of
[CuL](ClO4)2 and complexes [NaL](NCS) [1] and [ErL(H2O)(NO3)3] [2] is made.
1. A.Yu. Tsivadze, V.E. Baulin, N.M. Logacheva, L.Kh. Minacheva, I.S. Ivanova, V.S. Sergienko,
Zh. neorg. khim., 2007, 52, 2, 212-220.
2. L.Kh. Minacheva, I.S. Ivanova, I.K. Kireeva, V.E. Baulin, V.G. Sakharova, A.Yu. Tsivadze, V.S.
Sergienko, Zh. neorg. khim, 2000, 45, 2, 346-354.
The work was financially supported by the Russian Foundation for Basic Research (Grants № 1203-00991 and № 14-03-00100)
279
P169
SYNTHESIS OF ZINC AND COPPER COMPLEXES WITH
ETHYLENEDIAMIN-N,N-DI-3-PROPIONIC ACID
N.V. Tsirulnikova1, O.N. Podmareva2, E.S. Dernovaya1, I.V. Ananev3, V.V. Podgorsky2
1 - Federal State Unitary Enterprise «Research Institute of Chemical Reactants and Ultrapure
Compounds (IREA)»
2 - Federal Medical & Biological Agency SRI of Physical-Chemical Medicine
3 - A.N. Nesmeyanov Institute of Organoelement compounds Russian Academy of Sciences
Zinc and copper complexes of carboxyl and phosphorus containing complexons are known as
source of zinc and copper in chelate form.
To expand the sources of zinc and copper in the form of chelates, which are used in various fields of
science, medicine, pharmaceutics, agriculture and others, new compounds zinc and copper
complexes of ethylenediamin-N,N-di-3-propionic acid (asEDDP) were obtained.
New substances and method of their synthesis are suggested.
The method is based on interaction asEDDP with oxides of corresponding cations on the following
scheme:
, M=Zn, Cu
Structures of synthesized compounds M(asEDDP) were confirmed by elemental analyses, NMR
and IR spectroscopy data, X-ray structure analysis.
Ethylenediamin-N,N-di-3-propionic acid was synthesized by destruction of (ethylenediamine-N,Ndi-3-propionato)zinc(II) dichloride (Zn(asEDDP)Cl2), which was obtained by interaction zinc
chloride, ethylenediamine and acrylic acid [1].
Based on 1Н NMR spectroscopy of a samples of the reaction mass, received during process of
obtaining Zn(asEDDP)Cl2 with template synthesis and installed for the first time crystal structure of
dichlor(ethylenediamine)zinc(II) – the matrix of template synthesis, the mechanism of the formation
asEDDP was suggested.
Destruction of the Zn(asEDDP)Cl2 was carried out with chromatographic column filled by cation
exchange resin KU-2-8 in H+ form; elution was carried out with aqua ammonia. Using 1H NMR
spectroscopy and paper electropherography was shown that the process of obtaining asEDDP in
alkaline conditions is accompanied by decarboxylation to form a mixture of acrylic acid,
ethylenediamin-N-3-propionic acid and low-grade ethylenediamine of by the method of ion
exchange.
The newly synthesized derivatives can show promising biological activity.
It is well-known that complexes of Cu are able to take part in combination therapy and realize
effective correction of socially important neurodegenerative pathologies by means of regain
disturbed homeostasis of Cu(II).
Also, the obtained complex of Zn may be of interest as potential insulinomimetic substances. It will
be tested in Scientific-educational center of applied chemical and biological research at Perm state
Polytechnic University.
[1] Podmareva O.N., Tsirulnikova N.V., Fetisova T.S., Starikova Z.A. Method of synthesis of
asymmetric ethylendiamine-N,N-dipropionic acid. Patent 2507195 from 20.02.2014.
280
P170
THE SEVERAL ANTIBIOTICS PRODUCED BY EXPERIMENTAL STRAIN
STREPTOMYCES ROSEOFLAVU WERE STUDIED BY NMR
SPECTROSCOPE AND OFFERED THE MOST LIKELY STRUCTURES
D.E. Tsvetkov1, A.S. Shashkov1, А.О. Chizhov1, O.A. Lapchinskaya2, V.V. Kulyaeva2, G.B.
Fedorova2, A.S. Trenin2, E.G. Gladkikh2, V.V. Pogozheva2, M.O. Makarova2, G.I. Orlova2, G.S.
Katrukha2, N.E. Nifantiev1
1 - N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
2 - Gause Institute of New Antibiotics at RAMS, Bolshaya Pirogovskaya, 11, 119021 Moscow,
Russia
In the course of screening for new antibiotics producing breeding methods was selected strain
Streptomyces roseoflavus producing several macromolecular glycopeptide compounds whose
structure comprises a chain of amino acid residues and carbohydrate residue. Antibiotics in this
group have activity against gram-positive bacteria and mycobacteria, including Mycobacterium
tuberculosis. These compounds were isolated from the culture by extraction with organic solvents,
and then purified by HPLC method. Their structures were studied by mass spectrometry and 1H
NMR and 13C, COSY, HMBC, ROESY correlation spectroscopy. On the base of the data obtained
some assumptions were made about the possible structures of the active components.
281
P171
Pd(0)-CATALYZED DIASTEREOSELECTIVE HYDROGENATION OF 3METHYLIDENE-2-[(1S)-1-PHENYLETHYL]ISOINDOLIN-1-ONE IN CO2CONTAINING MEDIA
Zh.R. Sagirova, I.V. Kuchurov, O.V. Turova, E.V. Starodubtseva, S.G. Zlotin, M.G. Vinogradov
Zelinsky Institute of Organic Chemistry
Supercritical CO2 attracts considerable interest as a solvent for organic synthesis due to its
accessibility and convenience for “green chemistry”. In this context, an effective environmentfriendly methodology for Pd-catalyzed diastereoselective hydrogenation of 3-methylidene-2-[(1S)1-phenylethyl]isoindolin-1-one (1), a model heterocyclic substrate incorporating a chiral inductor,
has been elaborated. According to that, the CO2-expanded ionic liquid (IL) containing the dissolved
substrate and dispersed Pd (palladium acetate was used as a catalyst precursor) is a preferable
reaction system for this transformation. High values of conversion (~100%) and diastereoselectivity
(80% de) have been attained when the reaction was carried out in a three-phase system composed of
scСО2, СО2-expanded solution of 1 in [bmim]+OTf – and Pd(0). Surprisingly, in the absence of CO2
the conversion was significantly worse.
O
O
Ph
H2/Pd
Me CO2-expanded
ionic liquid
CH2
N
Ph
N
* Me
Me
CO2-containing
medium
Conversion
(%)
de (%)
[bmim]+OTf –
10
–
[bmim]+OTf – – СО2
100
80
[bmim]+BF4– – СО2
100
52
[bmim]+PF6– – СО2
100
45
bmim - 1-butyl-3-methylimidazolium, molar ratio [IL]/[1] = 6, [1]/[Pd(OAc)2] = 50, p(H2) = 20
аtm, p(total) = 120 atm, 50 °C, 2 h.
282
P172
NOVEL NICKELACARBORANES BASED ON NIDO-5,6DICARBADECABORANE
A.P. Tyurin, A.Yu. Kostyukovich, E.V. Balagurova, I.V. Pisareva, A.F. Smol’yakov, F.M.
Dolgushin, I.T. Chizhevsky
A.N.Nesmeyanov Institute of Organoelement Compounds of the RAS, 28 Vavilov Street, 119991,
Moscow, Russian Federation
As part of our systematic work on the reactivity studies of metallacarboranes of transition metals
with middle-cage carborane ligand based on nido-5,6-dicarbadecaborane (1), we synthesized and
characterized three novel types of nickelacarborane clusters: closo-3,1,2-{NiC2B7} (2 and 4),
isonido-1,2,4-{NiC2B8} (3) and closo-1,2,3-{NiC2B8} (5) (Scheme 1).
Scheme 1
The X-ray diffraction study of 2 revealed unusually long B(6)-B(9) distance of 2.000(6) Å.
Quantum-chemical calculations on DFT B3LYP/Gen (Gen - 6-311+G** for atoms C, H, B, P and
Dgdzvp for Ni) of its geometry were performed and, on this basis, the topology of electron density
distribution using Bader’s AIM (Atoms in Molecules) theory [1] was analyzed. The results of the
calculations suggested that there are no bond critical points (BCP) (3; -1) between atoms B(6)-B(9)
as well as between some other pairs of atoms such as Ni(2)-C(3), Ni(2)-B(5); B(4)-B(5), B(6)-B(7);
B(8)-B(9) and B(7)-B(8). Ring critical points (RCP) (3; +1) of four-membered faces, which do not
include metal atom, are characterized by negative Laplacian values (from -0.0540 to -0.0017 a.u.)
with electron density in BCP and RCP of the polyhedron having close values. Analogous
calculations for the other known in the literature closo-2,1,6-{RuC2B7} model, 2,2,2-(PH3)3-2,1,6closo-RuC2B7H9 [2], show quite similar distribution of critical points thus indicating significant
electron delocalization over the polyhedral surface in both structures.
1. Bader R.F.W. Atom in Molecules. A Quantum Theory, Clarendon Press, Oxford, UK, 1990, 438.
2. Bould J., Oro L.A., Macías R., Kennedy J.D., Londesborough M.G.S. Polyhedron. 2011, 30,
2140-2145.
Supported by the Russian Foundation for Basic Research (Project No. 12-03-00102).
283
P173
CHEMICAL TRANSFORMATIONS OF ALICYCLIC EPOXIDES
N.V. Vereshchagina, T.N. Antonova, S.A. Solovyovа
Yaroslavl State Technical University, Yaroslavl, Russia
The alicyclic epoxides are the basis for obtaining oxygen-containing compounds of different
functionality (alcohols, ketones, diols, aliphatic dicarboxylic acids). The appropriate catalyst allows
to obtain these compounds with high yield in the result of complex chemical transformations source
epoxides with the formation of an intermediate complexes of various structure.
Transformation of dicyclopentene epoxide (3,4-epoxitricyclo[5.2.1.02.6]decane) are of particular
interest for research [1, 2].
The reactivity of alicyclic epoxides of various structure (C8 – C10) in process of isomerization in
appropriate ketones with the use of catalysts – Lewis acids – has been investigated in this work. It is
shown that the presence of double bonds in the cycle increases the reactivity of molecule epoxide
C8. The isomerization unsaturated 5,6-epoxy-cis-cyclooctene leads to unsaturated ketone – 4-transcyclooctene-1-one – with good yield. By-products have been obtained using solvents in process of
isomerization. Selective formation specific ketone takes place only in the absence of solvent.
The results of kinetic researchs and the availability of induction period of isomerization reactions
indicate that the possible mechanism of the formation of the ketones includes donor-acceptor
interaction between the molecule catalyst and epoxide with the formation of an intermediate
complex II, as slow stage of process:
H
H al
O +
Li
H
H
H al
H
O
Li
O
Li
III
II
O
H
H
H al
H
H
I
+
Li
O
H al
H
H
Li
+
H al
V
IV
The redistribution of the electron density inside the complex II leads to a weakening the bond C-H
and C-O of reactive molecule epoxide. The sequential heterolytic breakup these bonds flowing
through formation of intermediate complexes III – IV, accompanied by the shift of proton and leads
to the disclosure of epoxy cycle with formation unsaturated ketone.
1 Vereshchagina, N.V. Alternative Methods for Production of Alicyclic Epoxides / N.V.
Vereshchagina, T.N. Antonova, I.G. Abramov, G.Yu. Kopushkina // Petroleum Chemistry –
2014, Vol. 54, No. 3, P. 207–212.
2 Antonova, T.N Catalytic Hydrogenation of Dicyclopentadiene to Dicyclopentene in the Liquid
Phase / T.N. Antonova, I.A. Abramov, V.Sh. Feldblyum, I.G. Abramov, A.S. Danilova //
Petroleum Chemistry. – 2009, Vol. 49, No. 5, P. 366 – 369.
284
P174
ELECTROCHEMICAL SYNTHESIS OF GERMANIUM ALKOXIDES
A.N. Vereshchagin, M.N. Elinson, I.V. Krylova, M.P. Egorov
N. D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
The wide applications of metal alkoxides, in particular in the preparation of various industrial oxide
materials, make the development of improved techniques for their production an urgent task. The
current methods of synthesis of M(OR)n, where n exceeds 2 are mostly based on exchange reactions
between MXn, (X may be Hal, R, H, NR2, N(SiMe3)2 etc.) and alkoxidizing reagents.1 These
reactions are multistep processes and the starting materials are difficult of access. In addition, they
involve various by-processes which contaminate the products and decrease their yields. For these
reasons, the direct electrochemical synthesis of metal alkoxides by anode dissolution of metals in
absolute alcohols in the presence of a conductive admixture seems a very promising method.
It is known few publications (mostly patents) devoted to the electrochemical synthesis of some
metal alkoxides.2-4
We have found that electrochemical dissolution of germanium anode in undivided cell in absolute
alcohol in the presence of sodium acetate as electrolyte under argon atmosphere results in formation
of germanium alkoxide.
Ge
Electrolysis
NaOAc / AlkOH
Ge(OAlk)4
H2S
GeS2
85-90%
EtMgBr
GeEt4
50-60%
A bubling of dry H2S through alcoholic solution of germanium alkoxide leads to germanium
sulphide in 85-90% yields. Liquid germanium alkoxides were isolated by distillation of alcohol
under argon atmosphere. Followed addition of ethyl magnesium bromide leads to formation of
tetraethyl germanium in 50-60% yields.
The developed electrochemical process represent a prominent one-step approach to germanium
alkoxide. Finally, the developed procedure utilizes simple equipment and undivided cell, and is
valuable from the viewpoint of environmentally benign synthesis and large-scale processes.
References
1. D. C. Bradley, in ‘Preparative Inorganic Reactions’, Vol. 2, ed. W. Z. Jolly, Interscience, 1965.
2. Patent DE 2349561A, 1974.
3. H. Lehmkuhl, W. Eisenbach Liebigs Ann. Chem., 1975, 672-691.
4. Patent CA1024466A1, 1978.
285
P175
MICROSIZED CERIUM CHLORIDE IS EFFECTIVE MICHAEL
CATALYST
V.A. Vil`, A.O. Terent`ev, I.A. Yaremenko, O.V. Bityukov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
The Michael reaction provides a commonly used and efficient synthetic route to C–C bond
formation. The synthesis involves the coupling of C-nucleophiles with unsaturated compounds
activated by an electron-withdrawing group. β-Dicarbonyl compounds comprise one of the largest
groups of C-nucleophiles. The latter are used to prepare products that are widely used in organic
synthesis.
In the present study, we found that microsized cerium chloride prepared from cerium chloride
heptahydrate catalyzes the coupling of β-diketones with vinyl ketones. The reaction products, β,δtriketones, are used in the synthesis of cyclic peroxides exhibiting antiparasitic activity and a wide
range of nitrogen-containing heterocyclic compounds, as well as oxabicyclic systems, which are
natural product analogues with antiparasitic activity.
It was found that the catalytic activity of cerium chloride widely used in organic chemistry depends
on the preliminary thermal treatment. The results of the present study suggest that this effect can
play a substantial role in the synthesis with the use of organocerium reagents.
References
1. Terent’ev A.O., Vil’ V. A., Yaremenko I. A., Bityukov O. V., Levitsky D. O., Chernyshev V. V.,
Nikishin G. I., Fleury F. Preparation of a Microsized Cerium Chloride-Based Catalyst and its
Application in Michael Addition of β-Diketones to Vinyl Ketones // New J. Chem., 2014, 38,
1493-1502.
286
P176
STEREOSELECTIVE SYNTHESIS OF THE PENTASACCHARIDES
RELATED TO THE FUCOIDAN FROM BROWN SEAWEED CHORDARIA
FLAGELLIFORMIS
D.Z. Vinnitsky, N.E. Ustyuzhanina, V.B. Krylov, N.E. Nifantiev
Laboratory of Glycoconjugate Chemistry, N.D.Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences, Moscow, Russia
Anionic polysaccharides fucoidans from brown seaweeds possess the different types of biological
activity such as anticoagulant, antithrombotic, anti-inflammatory, antiangiogenic and other
activities.1-3 Fucoidan chains are built up mainly of sulfated -L-fucopyranosyl residues, but the
fine structure of these biopolymers varies depending on seaweed species and growth conditions.
Such structural features as types of glycosidic bonds, degree and pattern of sulfation, presence of
branches and non-fucose residues were found to influence on the biological effect of fucoidans.1
To reveal the pharmacophores of fucoidans we perform the synthesis of the oligosaccharides related
to these biopolymers from different brown seaweed species. Here we report the synthesis of the
pentasaccharide 1 related to the fucoidan from the seaweed C. flagelliformis as well as its totally
sulfated derivative 2. The target compounds are built up of three (1→3)- linked α-L-fucopyranosyl
residues, the central of which bears disaccharide branch consisting of α-L-fucofuranosyl and α-Dglucuronyl units. Carbohydrate skeleton assembling of 1 and 2 was performed using di- and
monosaccharides 3-6. The block 6 was prepared by pyranoside-into-furanoside transformation4 of
the corresponding fucopyranoside precursor. All glycosylation reactions proceeded with high
stereoselectivity due to the presence of stereocontrolling groups in structures of glycosyl donors.
1. Cumashi, A.; Ushakova, N.A.; Preobrazhenskaya, M.E.; D'Incecco, A.; Piccoli, A.; Totani, L.;
Tinari, N.; Morozevich, G.E.; Berman, A.E.; Bilan, M.A.; Usov, A.I.; Ustuzhanina, N.E.;
Sanderson, C.J.; Kelly, M.; Rabinovich, G.A.; Iacobelli, S.; Nifantiev N.E. Glycobiology 2007,
17, 541-552.
2. Ustyuzhanina, N. E.; Bilan, M. I.; Ushakova, N. A.; Usov, A. I.; Kiselevskiy, M. V.; Nifantiev,
N. E. Glycobiology 2014, 24, in press.
3. Pomin, V.H. Biochim Biopys Acta 2012, 1820, 1971-1979.
4. V. B. Krylov, D. A. Argunov, D. Z. Vinnitskiy, S. A. Verkhnyatskaya, A. G. Gerbst, N. E.
Ustyuzhanina, A. S. Dmitrenok, J. Huebner, O. Holst, H.-C. Siebert, N. E. Nifantiev, 2014,
submitted.
287
P177
THE CATALYTIC ACTIVITY OF Ni-RANEY INTO THE
HYDROGENATION REACTION OF PYRAZOLINES
L.I. Vlasova1, V.A. Dokichev1, V.D. Sitdikov2, I.V. Aleksandrov2, V. Yu. Gordeev3, Yu. V.
Tomilov4
1 - Institute of Organic Chemistry, Ufa Scientific Center RAS; Organic Cchemistry; Ufa, Russia
2 - Ufa State Aviation Technical University, Department of Physics, Ufa, Russia
3 - Ufa State Aviation Technical University, Department of Engineering Technology, Ufa, Russia
4 - N. D. Zelinsky Institute of Organic Chemistry RAS, Laboratory of Chemistry of Diazo
Compounds, Moscow, Russia
The catalytic hydrogenation of pyrazolines in the presence of Ni-Raney that is proceeding with a
rupture of N-N bond, is a convenient method of synthesis of 1,3-propylenediamines and 3aminopyrrolidones, which exhibit the activity against of Alzheimer's disease, various tumors and
cancer cells, and they are perspective as a antiarrhythmic drugs [1].
In the present work we investigated the hydrogenation reaction of pyrazolines different structure in
the presence of Ni-Raney and the effect of nature Ni-Al alloy on the yield and the isomeric
composition of the resulting 1,3-propylenediamines and 3-aminopyrrolidones. Experiments were
carried out in a steel autoclave at 100 °C and a hydrogen pressure of 75 atm in the presence of 10
wt.% catalyst. The exit of hydrogenation products was 55-97%.
R2
H2 / Ni
R1
H2 N
R3
R1
N
R2
NH2
N
H
NH2
R2
H2 / Ni
R1 = CO2Me
C
R3
N
O
H
Figure 1. The image of nickel-aluminum alloy
On an example of methyl 4-phenyl-4,5-dihydro-1H-pyrazole-3-carboxylate, it is shown, that the
hydrogenation proceeds at a high yield (97%) and selectivity (ratio of cis- and trans-isomers of 1:
21) when using a Ni -Al alloy containing 49% NiAl3 and 51% Ni2Al3. N-substituted pyrazolines, in
the conditions chosen by us, do not react into the hydrogenation reaction.
1. Patent RU 2281938.
288
P178
BINDING OF Ni(II) IONS TO CHITOSAN AND ITS N-HETEROCYCLIC
DERIVATIVES: THEORETICAL AND EXPERIMENTAL STUDY
A.P. Portnyagin, S.Yu. Bratskaya, A.V. Voit
Institute of chemistry FEB RAS, Vladivostok, Russia
Fast expansion of chitosan application in the fields, where good chelation properties of polymers are
required, has significantly promoted interest to experimental and theoretical investigations of metal ions
interactions with native and chemically modified chitosans, and to the development of new procedures for
synthesis of derivatives with increased sorption capacities and enhanced selectivity. While decades ago the
main interest in this type of interactions was focused on the environmental application of chitosans for heavy
metals recovery, now complexation of metal ions with chitosan and its derivatives is considered as an
important stage in formation of metal nanoparticles in chitosan matrix for catalytic and optical applications.
These interactions are also important for understanding of the mechanisms of antibacterial, antifouling, and
antitumor activity of chitosan-metal complexes.
There are two main coordination models of ion binding to chitosan: “bridge model”, which describes
intermolecular coordination of metal ions with several amine groups, and “pendant model”, which describes
binding of the metal ion to a single amine group as a pendant. The most favorable coordination model –
“bridge” or “pendant” – is still disputable.
In this work we present theoretical study of Ni(II) ions binding to chitosan and its N-heterocyclic derivatives
with 4-pyridylethyl (PEC-4), 2-pyridylethyl (PEC-2) and imidazole (IMC) moieties, which now attract
attention due to the wide range of their functional properties. Trends in energies of complex formation in
dependence of type of functional substitute in chitosan found by DFT calculations have been compared with
experimental data obtained in sorption experiments using a series of chitosan derivatives. It was shown that
bridge complexes are more stable than pendant. Among the bridge models, structures that consist of
substituted and unsubstituted chitosan residue are more stable than complexes that consist of two substituted
residues. Substituted chitosan residues can be placed into the row according to their stability: IMC≥PEC2>PEC-4≈Native. The higher stability of IMC and PEC-2 complexes with nickel can be assigned to the
strong Ni-N bonds with heterocyclic nitrogen and chelate effect. These factors are not fully implemented in
the complexes of PEC-4 that’s why there are no great advantages compared to native chitosan. The most
stable complex is [Ni-IMC2]2+. Analyzing the atomic charges it was shown that charges on oxygen atoms of
hydroxyl groups, which are bonded to nickel cation, differ
very small from each other and don’t correlate with energy 1.55 QNi, e
of complex formation. Nitrogen atom charges can be
divided into 3 groups – the highest charge on amine group 1.50
atoms, a bit lower charge on imino group nitrogen atom
and the lowest charge on heterocyclic nitrogen atoms. 1.45
More interesting behavior is observed when nickel atomic
charges are considered that elucidates the charge transfer 1.40
from ligands to central ions. The relation between Ni
charge and relative formation enthalpy is presented on 1.35
Figure. The good correlation between these two parameters
is obvious. Therefore one can make a conclusion that not 1.30
only bonding atoms (N, O) participate in charge transfer
-250
-200
-150
-100
-50
0
from ligands to central ion but other ligand atoms also play
H', kJ/mol
a role.
Dependence of the Ni ion effective charge
on the relative enthalpy of complexes
formation.
289
P179
SYNTHESIS OF FLUORINATED BENZOQUINOLONES,
NAPHTHYLPYRIMIDINES AND NAPHTHYLDIHYDROPYRAZOLES
BASED ON CHEMICAL TRANSFORMATIONS OF 2,3
DIFLUORONAPHTHALENE
N.V. Volchkov, M.B. Lipkind, M.A. Novikov, O.M. Nefedov
N.D. Zelinsky Institute of Organic chemistry of Russian Academy of Sciences, Leninsky prospect
47, 119991, Moscow, Russian Federation
For the purpose of search new biologically active compounds methods for the synthesis of
fluorinated benzoquionolones with different fusion type of naphthalene and pyridone fragments
(compounds 2-4) as new structural derivatives of fluoroquinolone antibacterial drugs were
developed. Series of fluorine-containing 2-amino-4-naphthyl-6-arylpyrimidines (compounds 5-7) as
potential antibacterial and antifungal substances were prepared. Fluorinated 3-naphthyl-5-aryl- and
3,5-dinaphthyl-4,5-dihydro-(1H)-pyrazoles (8-10) as cytotoxic compounds were also synthesized.
O
C O 2H
R
Ar
N
N
F
R
N
F
1
F
2
650°C
C H C lF 2
R = H, Me
F
f lo w
1
NH2
5
F
R = E t, B z , c y c lo - C 3 H 5
Ar
F
O
N
C O 2H
F
R
6
NH2
1
N
N
F
H
F
Ar
R
F
F
3
7
Z
HN
C O 2H
N
F
F
N
F
NH2
N
O
Ar
F
N
4
Z = O , C H 2, N M e
N
9
Me
8
Ar
F
O
N
Ar
N
N
Me
O
F
F
10
N
Me
O
Developed synthetic ways are based on common starting compound 2,3-difluoronaphthalene 1,
prepared by соpyrolysis of CHCF2 and styrene1,2, and subsequent efficient introduction of various
functional groups (NO2, NR2, CO2H, COMe, CHO) in different positions of 2,3difluoronaphthalene structure.
References
1) O.M. Nefedov, H.V. Volchkov. Mendeleev Comm., 2006, 121-128.
2) O.M. Nefedov, A.A.Ivashenko. USSR Inventor’ Certificate, N 290,900, 1971.
290
P180
TRANSITION METAL CATALYZED ARYLATION OF PHOSPHORYLSTABILIZED CARBANIONS: A CONVINIENT APPROACH TO
α-FUNCTIONALIZED (ARYLMETHYL)PHOSPHONATES
M.O. Volkova, A.Y. Mitrofanov, N.S. Goulioukina, I.P. Beletskaya
Moscow State University, Department of Chemistry, Moscow, Russia
(Arylmethyl)phosphonates containing electron-withdrawing group such as an ester, cyano,
dialkoxyphosphoryl, or nitro group on the α-carbon are of considerable interest as versatile reagents
for organic synthesis. These compounds are vital starting materials for the Horner–Wadsworth–
Emmons reaction or the Michael addition and the presence of functional groups provides additional
synthetic potential.
In this study a series of α-functionalyzed (arylmethyl)phosphonates was synthesized under the
Hurtley1 reaction technique by the direct copper-catalyzed arylation of methanephosphonates,
bearing additional EWG-group (CN, COOEt, PO(OEt)2) (Scheme 1).
Scheme 1. Copper-catalyzed arylation of α-functionalized methanephosphonates.
It turned out that in each case a fine adjustment of catalytic system is necessary depending on the
nature of functional group present. Optimization of the reaction conditions (ligand type, base,
solvent, etc.), scope of aryl iodides used and possibility of further in situ product modification (e.g.
Scheme 2) will be discussed.
Scheme 2. One-pot synthesis of α-functionalyzed phosphonates comprising quaternary α-C atom.
We have also developed conditions for the palladium catalyzed cross-coupling of diethyl
nitromethylphosphonate with aryl iododes. A key requirement was found to be the proper choice of
phosphine ligand (Scheme 3).
This work was supported by the RFBR (grant № 12-03-93114) and was carried out in the
framework of the International Associated French–Russian Laboratory LAMREM.
[1] I. P. Beletskaya, A. Yu Fedorov, Modern Copper-Catalyzed Hurtley Reaction: Efficient CArylation of CH-Acid Derivatives, in Copper-Mediated Cross-Coupling Reactions (eds G.
Evano and N. Blanchard), John Wiley & Sons, Inc., Hoboken, NJ, USA, 2013, ch. 8.
291
P181
A THEORETICAL AND EXPERIMENTAL STUDY OF AN UNUSUALLY
STRONG HYDROGEN BOND IN A SALICYLAMIDE COCRYSTAL
A.V. Voronin1, M.V. Vener2
1 - G.A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences
2 - D.Mendeleev University of Chemical Technology of Russia
Solubility is one of significant parameters that have an impact on drug therapeutic effectiveness. At
the present time, a new method to improving solubility by two-component crystal engineering has
gained increased interest1. These species, known more commonly as pharmaceutical cocrystals,
consist of an active pharmaceutical ingredient and a second component which is safe for human
consumption. If the second component is solid at ambient conditions, the terms “a cocrystal” and “a
salt” are used. The latter term is referred to the species formed by ions, while “the cocrystal”
denotes a complex of non-ionized molecules2. The considered crystals usually consist of the H, C,
N, O and F atoms. Therefore, the ionized molecules appear due to the intra- or intermolecular
proton transfer. This phenomenon is associated with existence of the short (strong) hydrogen bonds
(H-bonds) with energies larger than 60 kJ/mol3. The different strength of H-bonds in the salts and
cocrystals leads to different properties of the resulting solid. The problem of obtaining the twocomponent crystal in desired ionization state is being widely studied in recent years4. Adequate
description of the structure and properties of the two-component crystals with strong H-bonds
requires the combined use of the experimental and computational approaches.
The new (2:1) cocrystal of a non-steroidal anti-inflammatory drug salicylamide with the oxalic acid
is used as an object of the present study. According to the Cambridge Structure Database analysis,
only 0.9% of all molecular complexes with ΔpKa of components > 4 form cocrystals instead of
salts5. ΔpKa equals to 7.14 for the cocrystal under consideration.
According to single crystal X-Ray, the salicylamide cocrystal possesses an unusually short O-H...O
intramolecular H-bond with O...O distance of 2.493 Å. The pattern of noncovalent interactions has
been quantified using the solid-state DFT computations (B3LYP/6-31G**) followed by the Bader
analysis of the periodic electron density. The lattice energy of the cocrystal is evaluated in a way
described in Ref. 6 to be equal to 314.7 kJ/mol. It is found that O-H...O and N-H...O hydrogen
bonds provide nearly 70% of all lattice energy in crystal. The IR spectrum computed in the
harmonic approximation using solid-state DFT agrees with the experimental spectrum of the
crystal. The IR intensive band around 2400 cm-1 is caused by the stretching vibration of the OH
group, involved into formation of the short (strong) H-bond.
[1] a) A.V. Trask, W.D.S. Motherwell, W. Jones. Physical stability enhancement of theophylline via
cocrystallization. Int. J. Pharm. 2006, 320, 114–123. b) N. Schultheiss, A. Newman. Pharmaceutical cocrystals and their physicochemical properties. Cryst Growth Des., 2009, 9(6), 2950–2967.
[2] F. Lara-Ochoa, G. Espinosa-Pérez. Cocrystals Definitions. Supramol. Chem., 2007, 19(8), 553–557.
[3] T. Steiner, The Hydrogen Bond in the Solid State, Angew. Chem. Int. Ed. 2002, 41, 48–76.
[4] C.B. Aakeroy, M.E. Fasulo, J. Desper. Cocrystal or salt: does it really matter? Mol. Pharm., 2007, 4(3),
317–322.
[5] A.J. Cruz-Cabeza. Acid-base crystalline complexes and the pKa rule. CrystEngComm, 2012, 14, 6362–
6365.
[6] A.N. Manin, A.P. Voronin, N.G. Manin, M.V. Vener, A.V. Shishkina, A.S. Lermontov, G.L. Perlovich,
Salicylamide Cocrystals: Screening, Crystal Structure, Sublimation Thermodynamics, Dissolution and
Solid-State DFT Calculations, J. Phys. Chem. B, 2014, 118, 6803–6814.
292
P182
OXYPALLADATION-HECK TANDEM REACTIONS OF INTERNAL
ALKYNES WITH ALLYLIC ALCOHOLS: A NEW APPROACH TO
ISOCOUMARINS AND BENZOPYRANS
M.-F. Zheng, W.-Q. Wu, H.-F. Jiang
South China University of Technology, School of Chemistry and Chemical Engineering,
Guangzhou, P. R. China
Transition metal-catalyzed cascade reactions have emerged as a valuable approach for the synthesis
of complex molecular structures and attracted great attention.1 In this regard, the electrophilic
activation of the alkynes by coordination to palladium continues to be a fascinating arena due to its
high efficiency in constructing multiple new chemical bonds in one step.2
Recently, a new approach for isocoumarins and benzopyrans between internal alkynes and allylic
alcohols is developed. This one-pot cascade cyclization is supposed to go through a sequential
intramolecular C−O bond cyclization, olefin insertion, β-H elimination and isomerization to afford
the isocoumarin products, all occurring in a single operation. Remarkably, benzopyran derivatives
could be also constructed efficiently via this cascade transformation (Scheme 1).
Scheme 1
Reference:
1. (a) Waslike, J.-C.; Obrey, S. J.; Bake, R. T.; Bazan, G. C. Chem. Rev. 2005, 105, 1001. (b)
Tietze, L. F. Chem. Rev. 1996, 96, 115. (c) Nicolaou, K. C.; Edmonds, D. J.; Bulger, P. G.
Angew. Chem. Int. Ed. 2006, 45, 7134.
2. (a) Frühauf, H.-W. Chem. Rev. 1997, 97, 523. (b) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan,
R. J. Chem. Rev. 1996, 96, 635.
293
P183
EFFICIENT SYNTHESIS OF PYRAZOLES VIA COPPER-CATALYZED
RELAY OXIDATION STRATEGY
X.-D. Tang, W.-Q. Wu, H.-F. Jiang
South China University of Technology, School of Chemistry and Chemical Engineering,
Guangzhou, P. R. China
Pyrazoles are an important heteroaromatic ring for pharmaceutical industry. Selected
pharmaceutical examples include the well-known drugs Mavacoxib, Celebrex, and Acomplia. Many
methods have developed for this attractive scaffold, and the classical preparation method is the
condensation of 1,3-dicarbonyl compounds and their 1,3-dielectrophilic equivalents with
hydrazines. However, they often suffer from some drawbacks such as multi-step synthesis, long
reaction time, use of expensive reagents, and the limitation of the substrates.
In the past several years, oxime esters have become powerful tool for N-heterocycles in presence of
Cu catalysts. Based on our continue interest in oxime esters, herein, we present a Cu-catalyzed
synthesis of 1,3- and 1,3,4-substituted pyrazoles from oxime acetates, anilines and formaldehyde
(Scheme 1c). This process involves Cu-catalyzed N-O bond cleavage, C-C/C-N/N-N bond
formation and oxidative dehydrogenation process, which is a relay oxidation process and the
oxidants are oxime acetates and O2.
Scheme 1
References
[1] Tang, X.; Huang, L.; Qi, C.; Wu, W.; Jiang, H. Chem. Commun., 2013, 49, 9597.
[2] Huang, H.; Ji, X.; Tang, X.; Zhang, M.; Li, X.; Jiang, H. Org. Lett. 2013, 15, 6254.
[3] Tang, X.; Huang, L.; Qi, C.; Wu, X.; Wanqing Wu, W.; Jiang, H. Chem. Commun. 2013, 49,
6102.
[4] Tang, X.; Huang, L.; Xu, Y.; Yang, J.; Wu, W.; Jiang, H. Angew. Chem. Int. Ed. 2014, 53, 4205.
294
P184
SELECTIVE SYNTHESIS OF CYCLIC PEROXIDES FROM TRIKETONES
AND H2O2
I.A. Yaremenko, V.A. Vil`, I.B. Krylov, A.O. Terent`ev
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp.,
119991 Moscow, Russian Federation
In the past decades, the chemistry of organic peroxides has attracted considerable attention from
physicians and pharmacologists because these compounds were found to have antimalarial,
antihelmintic, and antitumor activities. The interest in the synthesis of radical polymerization
initiators and drugs gave impetus to the development of methods for the synthesis of peroxides with
the use of carbonyl compounds, their derivatives, and H2O2 as the starting reagents.
A method for the assembly of tricyclic structures containing the peroxide, monoperoxyacetal, and
acetal moieties was developed based on the acid-catalyzed reaction of β,δ-triketones with H2O2.
The tricyclic compounds are produced in 39−90% yields and can be easily isolated from the
reaction mixture. The reaction is scaled up to several grams.
The resulting tricyclic compounds are unusual in that they contain one acetal and two
monoperoxyacetal moieties, which are as a rule unstable and can undergo peroxidation in the
presence of water and hydrogen peroxide under acidic conditions, and acetals are susceptible to
hydrolysis (Scheme 1).
Scheme 1. Synthesis of Tricyclic Peroxides
To assess the resistance of tricyclic peroxides to reagents used in organic synthesis and to determine
the structures, which are interesting to test for biological activity, we performed the oxidation,
alkaline hydrolysis, amidation, and reduction (Scheme 2).
Scheme 2. Reactions of Tricyclic Peroxides
Tricyclic monoperoxides showed high antischistosomal activity against Schistosoma mansoni.
This work is supported by RFBR №14-03-00237.
Reference
Terent’ev A.O., Yaremenko I.A., Chernyshev V.V., Dembitsky V.M., Nikishin G.I. // J. Org.
Chem. 2012, 77, 1833-1842.
Terent'ev A.O, Yaremenko I.A., Vil' V.A., Dembitsky V.M, Nikishin G.I. // Synthesis. 2013, 45 (2),
246-250.
Ingram K., Yaremenko I.A., Krylov I.B., Hofer L., Terent'ev A.O., and Keiser J. // J. Med. Chem.
2012, 55 (20), 8700-8711.
295
P185
NEW LIGANDS BASED ON OXAMINIC ACID THIOHYDRAZIDES
V.N. Yarovenko, E.S. Zayakin, I.V. Zavarzin, M.M. Krayushkin
N.D. Zelinsky Institute of Organic Chemistry, RAS, Moscow, Russia
Convenient methods for the synthesis of poorly studied thiohydrazides of oxaminic acids 1 were
developed. Compounds 1 are of special interest as complexing structures as containing donor atoms
with both high (N,O) and low (S) electronegativity, due to which they can form fairly stable
coordination compounds with both “hard” and “soft” Pearson’s acids. New ligands 2-7 were
synthesized from oxaminic acid thiohydrazide derivatives.
R = Alk, Ar, Het
1
O
OH
H
N
R
N
N
N
HN
N
N
H
NH
N
RNH
S
S
N
NH
HN
NHR
S
O
2
O
O
3
O
4
S
S
NH
HN
R
R
O
O
H
N
R
R1
N
H
N
H
N
H
N
R
N
OH
5
R1
N
H
N
H
6
HN
N
N H2
O
S
NH
NHR
R2
296
7
P186
SYNTHESIS OF 8-H-PYRIMIDO[ 5,4-B] [1,4]-THIAZINE-5,5-DIOXIDE
DERIVATIVES
M.A. Prezent, I.V. Zavarzin
N. D. Zelinsky Institute of Organic Chemistry, Laboratory for Chemistry of Steroid Compounds,
Moscow, Russia
We showed for the first time that methanesulfonylacetonitrile 1 can interact with two molecules of
dimethylformamide acetal. The reaction proceeds at both methylene and methyl groups of 1 to form
condensation product 2. The latter smoothly reacts with binucleophiles, such as acetamidine and
guanidine to form new representatives of the pyrimidine series: 4-amino-5-sulfonylpyrimidines
3а,в,с.
N
R
N
O
DMA
O
S
O
O S O nucleophile
DMFA
N
N
N
1
N
2
N
3a-c
N
O
R
N
S
S
O
N
N
O
4a-c
R = H (a); Me (b); NH2 (c)
Heating of 3а,в,с in acetic acid results in heterocyclization to form bicyclic systems 4а,b,c.
New 4-amino-5-sulfonylpyrimidines 3а,в,с were thus obtained, as well as derivatives of earlier
undescribed system 8H-pyrimido[4,5-b] [1,4]-thiazine-5,5-dioxide 4а,b,c.
297
P187
A CRUCIAL ROLE FOR THE ESCHERICHIA COLI S4 O-ANTIGEN OACETYLATION IN THE BACTERIOPHAGE G7C RECEPTION
E.L. Zdorovenko1, N.S. Prokhorov2, O.G. Ovchinnikova1, A.S. Shashkov1, A.V. Letarov2, Y.A.
Knirel1
1 - N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
2 - S.N. Vinogradsky Institute of Microbiology, Russian Academy of Sciences, Moscow, Russia
The phage–host system E. coli 4s–bacteriophage G7C was isolated from horse feces in 2006.
Despite an extremely narrow host range, E. coli 4s being the only known G7C host, the phage
persisted in the same horse population for several years. Evaluation of the fine mechanisms of the
G7C interactions with the host cell is important for understanding this ecological phenomenon.
Studies of G7C adsorption proteins suggested that the bacterial lipopolysaccharide is the primary
phage receptor. In this work, we studied structure and genetics of biosynthesis of the polysaccharide
chain of the lipopolysaccharide (O-antigen) in wild type E. coli 4s and its G7C-resistant mutants
4sI-2 and 4sI-4 that kept the ability to produce a long-chain O-antigen. The 4s O-antigen was found
to be related to that of E. coli O22 differing only in decoration of the linear polysaccharide with an
-D-Glc group on GlcA. The O-antigen of both mutants had the same structure as that of the wildtype strain but lacked O-acetylation on GalNAc.
E. coli 4s and O22 possessed essentially identical O-antigen gene clusters, which included all genes
that were necessary for biosynthesis of the E. coli O22 polysaccharide, including a gene for the
O-acetylation of GalNAc called wclK. In addition, E. coli 4s, but not E. coli O22, had a three-gtr
gene operon that was putatively responsible for the glucosylation of the O-antigen. In both 4sI-2
and 4sI-4 mutants, the wclK gene was inactivated by an insertion of a IS1-like element, the genetic
basis that accounted for the lack of the O-antigen O-acetylation. Complementation of the mutants
with the wclK gene from E. coli 4s restored the phase-sensitive phenotype.
The data obtained demonstrated that the O-antigen of E. coli 4s is the specific receptor of
bacteriophage G7C and the O-antigen O-acetylation is necessary for the phage reception.
298
P188
NEW WAYS TO HALOPEROXIDES
A.T. Zdvizhkov, A.N. Kulakova, R.A. Pototskiy, P.S. Radulov, A.O. Terentev, G.I. Nikishin
N.D. Zelinsky Institute of Organic Chemistry, RAS, Laboratory for Studies of Homolytic Reactions,
Moscow, Russia
Organic peroxides are one of the most useful classes of organic compounds in different part of
human life. The most common application of these substances is polymer chemistry. Moreover, the
high anticancer and antihelminthic activities have been discovered recently. It makes researchers
invent new types of peroxides and new ways to them.
Substitution of halide atom seems huge part of organic synthesis. So we focused on synthesis of
halide-substituted peroxide. The system of I2/hydroperoxide was examined in addition to double
C=C bond reaction. It was found that type of product depends on I2-hydroperoxide ratio.
Noteworthy target iodoperoxides were obtained with huge excess of iodine. However, iodoalcohol
as side product formed inevitably.
This fact may be complained by cleavage of O-O moiety under iodide-anion action. To avoid
degradation of target product we suggested use N-halosuccinimides as halogenations agents. The
decision allows decrease of haloalcohol percentage. However, it have been founded employment of
N-halosuccinimides initiate a new reaction of radical halogenations of double C=C bond. The
problem was solved with adding of catalytic amounts of phosphomolibdic or phosphotungstic acids.
Described results have extremely value. Developed methods allow to synthesis wide number of
structures containing different halogen atoms and peroxide moiety.
This work was supported by the Russian Science Foundation (Grant 14-23-00150).
299
P189
MODELING METAL-CATALYZED CROSS-COUPLING AND ADDITION
REACTIONS USING COMBINED QUANTUM AND MOLECULAR
MECHANICS METHODS
A.A. Zeifman, F.N. Novikov, O.V. Stroganov, V.S. Stroylov, I. Yu. Titov, G.G. Chilov, I.V.
Svitanko, V.P. Ananikov
N. D. Zelinsky Insitiute of Organic chemistry, Moscow, Russia
We have developed a combined QM + MM FEP (free energy perturbation) protocol for modeling
metal-catalyzed reactions in explicit solvent media. First, QM calculations are employed to handle
reagent, transition state and product in vacuum, and then MM FEP is used to account for solvation
effects. In contrast to commonly used PCM, MM FEP allows to obtain a “true” solvation free
energy by accounting for all solvent-solute interaction at atomic level and by thermodynamic
averaging over entire statistical ensemble and thus potentially offers great advantages in precision
of calculations (standard error <1 kJ/mol) and comprehension of the entire process.
Proposed method was employed to study the free energy profile of the model reaction (final step of
Suzuki-Miyaura cross-coupling) in 5 different solvents (benzene, toluene, ethanol, DMF, water).
Trend in activation free energy change among solvents predicted by our method was in accordance
with conventional PCM calculations, but for total reaction free energy change quantitative
disagreement was observed. Detailed analysis revealed that Pd(PPh3)2, the final Pd-containing
product of reaction, formed energetically favored hydrogen bonds in water and ethanol which were
explicitly accounted by MM FEP but omitted in PCM calculations.
300
P190
COPPER-CATALYZED ALLYLATION OF HEM-DIFLUOROSUBSTITUTED ORGANOZINC REAGENTS
A.A. Zemtsov, V.V. Levin, A.D. Dilman, M.I. Struchkova
N. D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
The ability of CF2-fragment to serve as a bioisostere of ether oxygen or a carbonyl group attracted
great attention in medicinal chemistry.1,2 Several methods for the synthesis of the compounds,
containing difluoromethylene fragment, such as direct deoxofluorination of carbonyl group3 or
consecutive transformations of halodifluoromethyl ethers4 are already well-described. However,
these methods suffer from a number of disadvantages, including hazardous reagents (SF4, DAST) or
inefficiently long synthetic sequences. Recently we formulated a novel strategy for assembling
gem-difluorinated products from three independent components: nucleophile, electrophile and
difluorocarbene5.
We developed an extension of this methodology by using organozinc reagents as nucleophiles and
allyl halides as electrophiles in a one-pot consecutive manner.6 Organozinc halides are involved into
the reaction with difluorocarbene generating difluorinated organozinc reagents. The latter species
undergo regioselective allylation reaction in the presence of catalytic amount of copper (I) salt. This
reaction provides a convenient route to the different CF2-containing olefins by a formation of two
C-C bonds in a one step.
This work was supported by Russian Foundation for Basic Research (14-03-31253 mol_a).
1. Fluorine in Medicinal Chemistry and Chemical Biology; Ojima, I., Ed.; Wiley: Chichester, U.K.,
2009.
2. Meanwell, N. A. J. Med. Chem. 2011, 54, 2529−2591.
3. Al-Maharik, N.; O’Hagan, D. Aldrichimica Acta 2011, 44, 65−75.
4. Qing, F.-L.; Zheng, F. Synlett 2011, 1052−1072.
5. Levin, V. V.; Zemtsov, A. A.; Struchkova, M. I.; Dilman, A. D. Org. Lett. 2013, 15, 917−919.
6. Zemtsov, A. A.; Kondratyev, N. S.; Levin, V. V.; Struchkova, M. I.; Dilman, A. D. J. Org.
Chem. 2014, 79, 818−822.
301
P191
Cu-CATALYZED ARYLALKYLATION OF C-C DOUBLE BONDS: AN
EFFICIENT ROUTE TO ALKYL SUBSTITUTED OXINDOLES
Y. Yu, M. Zhang, H.-F. Jiang
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou
510640, P. R. China
Transition metal-catalyzed intramolecular or intermolecular oxidative difunctionalization of alkenes
has attracted more and more attention in recent years, since the introduction of diverse functional
groups into organic molecules can lead to lots of important innovations for synthetic chemistry. Upto-date researches presented that copper was an efficient, abundant, and inexpensive metal to
perform these reactions instead of rhodium, ruthenium or palladium catalysts. Compared with C-N,
C-O, C-Br bond formations, dicarbonation of C-C double bonds is less reported since a final C-H
cleavage is required.[1-3]
In order to expand the richness of copper-catalyzed difunctionalization of alkenes, we focus on the
study of dicarbonation of C-C double bonds. We herein report an efficient and highly regioselective
strategy for the construction of alkyl substituted oxindoles through the copper-catalyzed oxidative
annulation between potassium alkyltrifluoroborates with N-arylacrylamides (Scheme 1). It was
supposed that potassium alkyltrifluoroborate should be an alkyl radial precursor and played an
important role in this transformation.
Scheme 1
References
[1] Huang, L.; Qi, C.; Liu, X.; Jiang, H. J. Am. Chem. Soc. 2010, 132, 17652.
[2] Wang, Y.-F.; Zhu, X.; Chiba, S. J. Am. Chem. Soc. 2012, 134, 3679.
[3] Bovino, M. T.; Chemler, S. R. Angew. Chem. Int. Ed. 2012, 51, 3923.
302
P192
VERSATILE SYNTHESIS OF QUINOLINES FROM α-2-NITROARYL
ALCOHOLS AND ALCOHOLS VIA RUTHENIUM-CATALYZED
HYDROGEN TRANSFER STRATEGY
F. Xie, M. Zhang
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou
510640, P. R. China
In line with the principle of green chemistry, the application of abundant and sustainable alcohols as
both hydrogen suppliers and coupling components via hydrogen-transfer strategy is, in synthetic
chemistry, of important significance.1 Quinoline derivatives constitute a significant important class
of nitrogen-containing heterocycles. To date，a large number methods have been developed to
access various quinolines. However, many of these methods suffer the use of special pre-functional
or less environmentally benign halogenated reagents, which would increase the complexity of the
work-up procedure or result in detrimental influence on environment.2 Hence, the exploration of
straightforward methods for quinoline syntheses from easily available and eco-compatible reagents
still remains a demanding goal.
Herein, we report a new and straightforward method for versatile synthesis of quinoline derivatives
from stable and easily available α-2-nitroaryl alcohols and alcohols via ruthenium-catalyzed
hydrogen transfer strategy. In such as a synthetic protocol, two alcohol units and the nitro-group
serve as the hydrogen donors and hydrogen acceptor, respectively. Hence, there is no need for the
use of specialized reducing agents. By employing Ru3(CO)12/dppf/t-BuOK as an efficient catalyst
system, various substituted products can be furnished in reasonable to good isolated yields. The
transformation is operationally simple and there is no need for pre-functionalization (Eq.1).
Hydrogen donors
3
R1
2
R
R
OH
+
1 NO2
OH
R4
R3
1
R
R5
Ru cat
R5
2
(Eq.1)
R2
3
N
R
4
Hydrogen acceptor
Scheme 1. Ruthenium-catalyzed synthesis of various substituted quinolines fromα-2-nitroaryl
alcohols and alcohols.
References
1
(a) Gunanathan, C.; Milstein, D. Science 2013, 341, 249; (b) Michlik, S.; R. Kempe. Nat. Chem.
2013, 5, 140. (c) Michlik, S.; Kempe, R. Angew. Chem. Int. Ed. 2013, 52, 6326.
2
(a) Guillena, G.; Ramón, D. J.; Yus, M. Chem. Rev. 2010, 110, 1611. (b) Dobereiner, G. E;.
Crabtree, R. H. Chem. Rev. 2010, 110, 681. (c) Guillena, G.; Ramón, D. J.; Yus, M. Chem. Rev.
2009, 110, 1611.
303
P193
SYNTHESIS OF GLYCOLURYL NITRO DERIVATIVES IN LIQUID OR
SUPERCRITICAL CARBON DIOXIDE
M.N. Zharkov, I.V. Kuchurov, I.V. Fomenkov, S.G. Zlotin
N. D. Zelinsky Institute of Organic Chemistry, Laboratory of Fine Organic Synthesis, Moscow,
Russian Federation
Dinitroglycoluryl (DINGU) is a high-energy (VOD ~ 7580 m/s, d = 1,99 g/cm3), termally
(deflagration temp. = 225-250 С) and hydrolytically stable explosive that is used in low-sensitive
molding compositions with TNT as a substitute for the RDX. Commonly, it is synthesized by a
nitration of the glycoluryl and its derivatives with nitric acid, acetyl nitrate or mixed acids at 2065 °С under neat conditions where the temperature control is complicated and explosion risks are
high. Herein, we report an alternative procedure for the synthesis of glycoluryl nitro derivatives by
performing the nitration of N- or C-alkylglycoluryls with the dinitrogen pentoxide in liquid or
supercritical (sc) carbon dioxide. Dinitrogen pentoxide (N2O5) is an active nitrating agent, which
generates recoverable nitric acid as the only acidic by-product. Furthermore, carbon dioxide, being
an available, non-toxic, incombustible, and thermally stable compound with a high heat capacity in
liquid or supercritical state, is a highly suitable medium for nitration reactions.1
Under proposed conditions, dinitroglycoluryl derivatives 2a-c and 4 have been prepared in 56–89%
yield.
NO2
H R
N
N
H R H
N
N
O
O
N
N
H R H
1a-c
H3C
N
H3C
N
R H
O2N
2a-c (56-89%)
N2O5
CO2, 80-100 bar
5-45oC
O
N
O
N
H
N
O
O
H3C
NO2
N
N
N
N
O
O
N
H
H3C
3
1, 2: R = H (a), CH3 (b); R2-R2 = -(CH2)4- (c)
NO2
4 (73%)
The proposed nitration mode significantly reduces explosion risks due to the dilution of reaction
mixture with liquid CO2 resistant to the action of nitrating agents. Furthermore, it eliminates the use
of mixed acids that are associated with energy-consuming waste disposal and environment pollution
problems.2
The work was financially supported by the Presidium of Russian Academy of Sciences (Basic
Research Program No. 8) and the Russian Foundation of Basic Research (project 13-03-12223).
[1] I.V. Kuchurov, I.V. Fomenkov, S.G. Zlotin, V.A. Tartakovsky, Mendeleev Commun., 2013, 23,
81-83.
[2] I.V. Kuchurov, I.V. Fomenkov, S.G. Zlotin, V.A. Tartakovsky, Mendeleev Commun., 2014,
submitted.
304
P194
REACTION OF AMIDOXIMES WITH NITRILES AT HIGH PRESSURES
E.R. Kofanov1, S.V. Baikov1, A.A. Zharov2, G.A. Stashina2, I.V. Zavarzin2
1 - Yaroslavl State Technical University, Laboratory for Chemistry of Steroid Compounds,
Yaroslavl, Russia
2 - N. D. Zelinsky Institute of Organic Chemistry, Laboratory for Chemistry of Steroid Compounds,
Moscow, Russia
The reaction of nitriles with amidoximes affording 1,2,4-oxadiazoles under rigid conditions (at
180оС) in low yields has first been described in 19841. Later it was shown that the yield can be
increased and the temperature of the process can be decreased by using the catalyst, namely, the
ZnCl2/HCl system2,3
We assumed that the reaction of amidoximes with nitriles carried out under fairly high pressure
would allow one to decrease temperature and to reject the use of any catalysts and additional
reagents. The reaction of amidoximes (I, R=H, -OCH3, -NO2) with acetonitrile was studied under a
pressure of 10 Kbar. An acetonitrile excess was used as a solvent. The yield of the corresponding
1,2,4-oxadiazoles (II, R=H, -OCH3, -NO2) depends on the temperature, being 40-80% (Scheme 1).
N OH
N O
10 Kbar
R
I
R
CH3CN
NH2
N
II
CH3
In addition to 1,2,4-oxadiazoles II, the formation of the corresponding substituted 3,5-diphenyl1,2,4-oxadiazoles (III, R=H, -OCH3, -NO2) and 1,3,5-trimethyltriazine (IV) was detected in all
cases. However, the yields of these products were insignificant.
N
R
R
N
C H3
N
H3C
O
N
N
C H3
III
IV
The “Barostat” type setup that makes it possible to carry out investigations at pressures below 15
Kbar was used in the work4.
References
1. Weddige A, J. prakt. Chem. [2], 9, 132 (1874).
2. Yarovenko V.N., Taralashvili V.K., Krayuskin M.M., and Zavarzin I.V., Tetrahedron, 1990, Vol.
40, No. 11, 3941.
3. Yarovenko V.N., Shirinyan V.Z., Ugrak B.I., Krayuskin M.M., and Zavarzin I.V., Russ. Chem.
Bull., 1994, 43, 627.
4. Moskvin D.I and Zharov A.A., in “Preparative Organic Syntheses” (Collection of Works), Vol.
1. Moscow, 2006 (in Russian).
305
P195
CONVENIENT DOMINO SYNTHESIS OF POLYFUSED HETEROCYCLIC
COMPOUNDS FROM SIMPLE STARTING MATERIALS
A.A. Zubarev, N.A. Larionova, L.A. Rodinovskaya, A.M. Shestopalov
N. D. Zelinsky institute of organic chemistry, Leninsky prospekt, 47, 119991 Moscow, Russia
Previously we have developed a convenient method for the synthesis of thieno[3,2-b]pyridines from
malonitrile (1), carbon disulfide (2) and ethyl 4-chloroacetoacetate (4)1. The key step of this
reaction is to generate a solution of dipotassium 2,2-dicyanoetendithiolat (3), followed by its
selective monoalkylation. The selectivity has been achieved by using the Ruggli-Ziegler dilution
principle. Based on this approach, we have developed a convenient one-pot method for the
synthesis of new condensed heterocyclic systems, thieno[3',2' : 4,5]thieno[3,2-b]pyridins and
pyrimidins (6). The two consecutive domino reactions: type of the SN2 reaction → the ThorpeZiegler reaction → the Thorpe-Guareschi reaction, with the formation of thienopyridine system (5)
and then type of the SN2 reaction → the Thorpe-Ziegler reaction with second thiophene ring closure
for this method of synthesis have been used. By using the Ruggli-Ziegler dilution principle, we
have reversed order of construction of the heterocyclic system: first thiophene ring (7), and then
thienopyridine system have been formed (Shceme 1.)
Intermediate 7 is a convenient substrate for the synthesis of 2,5-unsymmetrically substituted
thienothiophens 8. By using in this synthesis of 2-bromo-(3`,4`,5`-trimethoxy)acetophenone, we
have obtained thienothiophens 9 - the first example of biheterocyclic analogues of natural
anticancer agent phenstatin. Based on thienothienopyridins 6 (X = CH), were have synthesized of 2amino-3-cyanopyrans 10, by using of domino reaction type of the Knoevenagel reaction → the
Michael reaction → the hetero-Thorpe-Zieglerreaction.
1.
A. M. Shestopalov, L. A. Rodinovskaya, A. A. Shestopalov., J. Comb. Chem., 2010, 12, 9.
306
P196
DIMETHYL ETHER - ALTERNATIVE MOTOR FUEL
F.A. Babayeva, R.Q. Ahmedova, X.D. Ibragimov
National Academy of Sciences of Azerbaijan The Y.H. Mamedaliyev Institute of Petrochemical
Processes
The important problem of the present is the alternative energy carrier searching. This is related not
only to oil stock deficit but also to ecology problems. Dimethyl ether is one of the perspective
energy sources by ecological viewpoint.
The perspectives of using DME as ecologically clean motor fuel alternative to oil and also ability of
transportation into low-molecular olefins C2-C4 and the components of high-grade petrol attracted
an interest of petrochemical scientists.
Properties of DME and presence it in oxygen atom composition provides the excellent cold start of
motor and abatement of noise. The main priority of DME as diesel fuel is ecologically clean
expulsion. Content of toxic components in it – lack of carbon-black, decreasing the substance of
nitric oxide – meet the ecological requirements of European standards.
We carried out researches focused on DME production from methanol, designed the conditions of
selective involvement of DME into the production process of low-molecular olefins C2-C4 and
¹ and atmospheric pressure. It was investigated the influence of temperature and weight hour
space velocity to product yield and process selectivity. Reaction products were analyzed on gas
chromatograph “Auto System XL” by Perkin Elmer, in the capacity of fixed phase there were used
5% methyl polyphenile siloxane.
Synthesized nanostructured catalyst Zn (5%) Al2O3 displays high activity in process of conversion
methanol into DME. On initial period of process, on first 20 minutes occurs the activation of
catalyst. Increasing of catalyst activation at the process of degidratational dimerisation of methanol
to DME connected to brendsted acidity changes of test specimen. Activity of catalyst doesn’t fall
during the experiment, DME yield reaches 98.42% at selectivity 99.4%.
It should be noted that the availability of using carbon dioxide for DME synthesis as potential
carbon source with simultaneous utilization of current greenhouse gas also is the effective problem
solving of environment and production development of DME is quite actual.
307
P197
NONTRADITIONAL APPROACHES AND PERSPERTIVE IDEAS OF
THERMODYNAMIC ANALYSES OF ORGANIC: CHALLENGES AND
INSIGHT
A.K. Baev
G.A.Krestov Institute of Solution Chemistry of the RAS, Ivanovo
Reflection of changing in structure of liquids, solutions on enthalpies and entropies of evaporation
provides possibility to perceive the peculiarities of intermolecular interactions and evaluate their
energies. But organic and elementorganic compounds with alkyl ligands are in oblivion on the
following reasons [1]:
it was created notion historically that intermolecular interactions in solutions of this compounds are
non-specific ones;
comprehensive model sp3-hybridization of electron configuration of carbon atom was not exposed
to doubt.
At this lecture we are discussed a contradiction between thermodynamic properties of evaporation
process of organic and elementorganic compounds of main groups elements obtained
experimentally and predicted by above-mentioned model and substantiated the following
regularities:
-substantiated refusal from sp3-hybridization in CH4 and molecules of elementorganic compounds
with alkyl ligand;
-additional orbital dative type interaction in electron structure of main group element compounds
with saturated hydrocarbon ligands and their coordination derivatives;
-pentacoordinated carbon atom in specific intermolecular interactions;
-employment of all bond vacancies in structure of molecules;
-enthalpy and entropy of evaporation are interconnected with number and energy of specific
intermolecular interactions [2].
The results of quantum chemical calculations of A(CH3)n structure are the base for refusal from
sp3-hybridization, which are used for conception development of reverse dative bonding between
carbon atom of alkyl ligand and central atom “A” of complex ARn. It is also established that:
-valent 2s2(C)-electron pair remains essentially localized on carbon atom even in CH4 molecule
and only two of four valent electrons of atom “C” situated on its three valent AO 2px, 2py, 2pz take
part effectively in hypervalent bonding with all of four hydrogen atoms;
-carbon atom of bridge CH3-group (in particular Al2(CH3)6) forms the fifth coordination with
second atom “A” by dative mechanism using own valent electron pair and vacant orbital of central
atom “A”. This principle correlates with the results of X-ray investigations of alkyl compound
structures [3].
In the lecture we discuss different types of specific intermolecular interactions with participation of
pentacoordinated carbon atom of alkyl compounds, functional solvents, hydrogen bonds of
formamide, alcohols, carbonic acids and calculations of their energies.
1. Baev A.К. Journal of Coordination Chemistry. 1996.V. 22. № 5. P. 399-402
2. Baev A K. General and Applied Chemistry. Minsk. Belarusia 1969. № 1.P.197
3. Baev A.K., Korolkov D.V., Book of Abstract the XVth FECHEM Conference on Organometallic
Chemistry. University of Zurich. Svizeland.(2003) 350.
308
P198
COMPLEX COMBINATIONS OF TRANSITIONAL METALS WITH
REDOXYLIGANDS - NEW TYPE CATALYST IN HYDROSILICATING
REACTIONS OF UNSATURATED SILICOORGANIC MONOMERS
T.M. Chigorina, A.A. Arutyunyants, E.A. Chigorina
North Ossetian State University, Vladikavkaz, Russia
The catalyst is one of the most important component vulcanizing systems, allowing influence upon
velocity of the vulcanizing, nature of the forming net, temperature and hardening depth, as well as
allowing to obtain compositions with the necessary set physical-chemical features.
In observed work catalysts of the fundamentally new type were synthesized - complex compounds
of the platinum group with redox-ligands, capable to monoelectronic reverse transition –
bensonytril-type complex compounds of platinum, palladium and rhodium.
The electrochemical characters and velocity of the complex obtained interaction with a classical
hydroxylate reagent – hydrid-containing silans, vinilsyloxans, were studied. The compositions,
basing the vinilsyloxan rubbers, hardened with the complex of platinum with redox-ligands, give
the small reconstruction peaks. The smaller eduction of the hydrogen occurs at cation-radical sylan fragmentation in comparison with the traditional catalyst (the systems based on platinum - a
Spayer catalysts).
It is shown for the first time that the role of the catalyst is to generate catyon-radical low-molecular
sylan, the further fragmentation of which leads to throwing out of atomic hydrogen and forming the
siliconium ion. The reaction hydrosylating runs by furcated chain reaction mechanism, platinum
anode - an initiator of the chain reaction.
The complex compounds of metal platinum group with redox-ligands - high viability, vulcanizing
velocity, high dielectric parameters; low temperature hardening (900 - 600С) compositions are
obtained under usage of high active catalysts synthesized. The main advantages of catalyst
synthesized are its reusability; lack of mixture spontaneous heating and temperature leap –
important for industrial conditions.
Noted that new hydrosilating catalyst – rhodium semiquinolate, – does not cause the metallic article
corrosion.
The physical-mechanical and electrical features of the polymetil-vinilsyloxan composition designed
under accelerated vulcanizing are following:
- conditional toughness, MPA - 1,5-5,0;
- relative lengthening -100-150 %;
- elasticity module, MPA - 1,7-2,2;
- dialectical losses tangent at frequency 106 Hz - 5·10-4 – 3·10-3;
- dialectical permeability at frequency 106 Hz - 3-3,5.
The correlation between electrochemical data and rubber hardening will allow offering the scientific
foundation for search of new effective, selective and sufficiently available catalyst to
polyconnection reactions.
The complexes synthesized so as materials designed on their fundament will find use in the
electronic technology items.
309
P199
THE IMMOBILIZED AND RECYCLE CATALYST FOR ASYMMETRIC
FRIEDEL-CRAFTS REACTION
V.G. Desyatkin, M.V. Anokhin, I.P. Beletskaya
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
In this work we obtained BOX-ligand 1, immobilized on the polymer matrix and tested catalytic
active of our catalyst.
As the polymer matrix, we chose commercially available Merrifield resin. The of BOX-ligand 1
immobilization on the polymer matrix was performed using the «click»-reaction. After the
treatment the polymer BOX-ligand 2 by copper (II) triflate catalyst 3 was obtained.
Polymeric catalyst 3 was used for asymmetric Friedel-Crafts reaction indoles and different Michael
acceptors (arylidenemalonates, arylidenepyruvate) and methyl 3,3,3-thrifluoropyruvate. Products of
reactions were obtained with high yields (up to 99%) and high enantiomeric excess (up to 99%).
The catalyst 3 was recycled of several times.
310
P200
SYNTHESIS AND INVESTIGATION OF NEW Zr AND Ti COMPLEXES
FOR OLIGOMERIZATION AND POLYMERIZATION OF THE ETHYLENE
A.A. Khanmetov, A.H. Azizov, M.J. Khamiyev, R.V. Aliyeva, A.D. Guliev
The Institute of Petrochemical Processes of Azerbaijan National Academy of Sciences
In recent years Zr and Ti complexes with ligands of different phenols are of great interest in the
polymerization and oligomerization of the ethylene [1-3].
In the abstract presents the results of the synthesis and investigation a new zirconium and titanium
complexes which obtained by interaction of ZrCl4 and TiCl4 with morfolylmethyl - 4 - methyl phenol, 2piperidinylmethyl-4-methyl phenol, 2-amino benzoic acid, 2-diethylaminomethyl -4-methyl phenol and 2{[2,6 di (isobutyl) phenyl] iminomethyl} phenol [4]. This Zirconium complexes were investigated by IQS,
DSK, and SEM. The IR spectra of the synthesized compounds presented absorption bands around 2547,
2573 and 2633 sm-1, corresponding to N+R3H ammonium group. The absorption band also contains around
530-600 sm-1,which characterizes the valence vibrations of Zr-O and Ti-O bonds. The pictures illustrate the
complex of ZrCl4 with 2 - piperidinyl aminomethyl - 4 methylphenol (pic1.a,b), which were obtained by the
scanning electron microscope. The freshly prepared complex (prior to reaction) has a well-developed
structure. As seen in pic.1b. (x 500F) after the reaction the surface remains sufficiently well developed. The
separate fragments of the complex closely interconnected into a single mass. The system has been very
porous and it is arranged lots of pores and channels which reacting components can be placed in the pores.
a)before reaction b) after reaction
Picture 1. Scanning electron microscope of Zr[4 – methyl 2-(O)-C6H3CH2NH(CH2)5Cl]2Cl2
The melting temperature of the synthesized complexes was determined by DSC. It was found that the
melting temperature of these complexes is changed within the limits 168 ÷ 195 0C.
It was established that the synthesis of the zirconium and titanium compounds with organoaluminum
compound ((C2H2)nAlCl3 - n, where n = 3÷1 at molar ratio of Zr : Al = 1 : (10 ÷ 50) leads to the formation of
supported ionic liquid in the complex catalytic system, which could be active in the oligomerization and
polymerization of the ethylene. A scientific opinion concerning the possibility of receiving polyethylene
having various molecular and thermodynamic properties has been presented and it is proved by experimental
method. Obtained polyethylene in the presence of titanium complexes is characterized by different molecular
and thermodynamic parameters. Crystallinity degree (was determined with DSK) - 42,27 – 72,9%, density –
0,94 – 97 g/sm3; Mw=170,2 x 103 – 473,5 x 103; Mn=3,9 x 103 – 180,7 x 103; Mw/ Mn= 2,62-93; Тm = 126,9
141,60C.
1. Vakshouri A.R., Azizov A.H., Aliyeva R.V., Kalbaliyeva E.S. Some patent developments in the field of
non – metallocene catalysts for ethylene(co) polymerization (review)// Azerbaijan Petrochemical and Oil
Refining 2009,v.38,10,p.148-166.
2. Xiao-Chao Shi and Guo-Xin Jin. Titanium and Zirconium catalysts with [N,O] ligands; synthesis,
characterization andtheir catalytic properties for olefin polymerization/Organometallics 2012, 31 pp.
7198-7205
3. Ke-Ming Song, Hai-Yang Gao, Feng-Shou Liu, Jin Pan, Li-Hua Guo, Shao-Bo Zai, Qing Wu/Catal.
Letter/.(2009) 131: p.566-573
4. Azerb. Pat.J 20080048(2008) Aziz A.G., Aliyev R.V., Rasulov Ch.K. et al.
311
P201
MODIFIED ALKYLPHENOLATE ADDITIVE TO THE MOTOR OIL
A.K. Kazimzadeh, E.A. Naghiyeva, A.A. Gadirov, R.A. Mammadova, S.I. Nasirova
A.M.Guliyev Institute of Chemistry of Additives of Azerbaijan National Academy of Sciences
(ANAS), Beyuk-Shor Str., Block 2062, AZ1029, Baku, Azerbaijan
The high speed in the development of modern machinebuilding produces the inereased
requirements to the quality of motor oils. One of the perspective direcfions of the motor quality
improvement is the introduction of the new efficient additives to their composition.
It is known that alkylphenolate additives are widely used as detergent - dispersant additives to the
motor oils. The introduction of different heteroatoms and functional groups to the composition of
additives molecule expands the range of their exploiatation action.
We are suggesting the method of obtaining of the new sulphurcontaining alkylphenolate additives
IXP-154 and IXP-162, representing carbonated calcium salts of condensation product of
dodesylphenol or mixture of dodesylphenol and alkylsalisylic acid with formaldehyde and sulphid
sodium respectively.
These additives technology production has a number of advantages as compared with industrial
sulfhurcontaining analogues (sulphuration is conducted at 95-980C against 170-1800C for industrial
samples and without H2S secretion).
The process of obtaining of IXP-154 and IXP-162 additives consists of the following stages:
- condensation of dodecylphenol (mixture of dodecylphenol and alkylsalisylic acid) with
formaldehyde and natriun sulphur.
- neutralization of condensation products by means of Ca(OH)2
- carbonation of neutralization products
- drying and centrafuqal carbonation products.
IXP-154 and IXP-162 additives have alcaly number of 150-170mqKOH/q.
The results of the research have shown that the obtained additives are multifunctional, giving to the
motor oils high anticorrosive, antioxidative, detergent properties and are better than industrial
additives ОLОА-218А and VNIINP-714(carbonated sulphurphenolate calcium)
for anticorrosive properties.
Besides, the additive IXP-162 excels additive IXP-154 in anticorrosive properties and thermal
stability, that, apparently, is provided by having in the composition of the additive of carboxilate
groups in combination with sulphur atom.
The additive have been investigated separately and in the composition of motor oils .
By using additives IXP-154 and IXP-162, and also industrial additives M-8B and M-10Г2 have
been developed which meet the requirements for these oils and don’t fall behind foreign analogues
of the firm shell in exploitation properties.
This with the usage of IXP-154 and IXP-162 it is possible to obtain new perspective motor oils
according to the simplified and ecologically harmless technology.
312
P202
SYNTHESIS AND NMR STUDY OF ADAMANTYL DERIVATIVES OF 1,5DIHYDROXY- AND 1,5-DIMETHYLNAPHTHALENES
I.V. Peterson, N.M. Svirskaya, A.A. Kondrasenko, A.I. Rubaylo
Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia
In continuation of studying structure and reactivity of various adamantyl derivatives of
dihydroxynaphthalenes with used NMR spectroscopy [1], we have investigated the interaction of 1adamantanol with 1,5-dihydroxy-(I) and 1,5-dimethylnaphthalene (II). As a result, there were
prepared: 3-(1-adamantyl)- (III) and 3,7-di(1-adamantyl)-1,5-dimethylnaphthalene (IV), and 3,7di(1-adamantyl)-1,5-dihydroxynaphthalene (V).
R1
R4
+
I - R1=R3=CH3; R2=R4=H
II - R1=R2=OH; R2=R4=H
R1
OH
R2
CF3COOH
a: (1:1)
b: (1:2)
R3
R4
IIIa - R1=R3=CH3; R2=Ad; R4=H
IVb - R1=R3=CH3; R2=R4=Ad
R2 Vb - R1=R3=OH; R2=R4=Ad
R3
Structure elucidation of III-V compounds and a full analysis of their 1H and 13C (600.13 and 150.71
MHz) spectra was carried out using COSY, HSQC, HMBC on NMR spectrometer «Bruker Avance
III 600» (Krasnoyarsk Regional Center for collective use SB RAS).
As an example of NMR studies, here presented HSQC spectrum of the compound IV (CD2Cl2).
This diadamatylsubstituted compound, as well as product V, is symmetrical, whereby the chemical
shifts of protons and carbons in opposite naphthalene rings are pairwise equal. In 1H spectrum is
appeared on presence in the aromatic region two doublets (δ 7.44 and 7.71 ppm) with J =1.6 Hz,
which indicated about their metha-position relative to each other and thus confirms connection of
the adamantyl group to position 3 and 7. Suitable cross-peaks with two signals (δ 116.9 and 124.5
ppm) in 13C spectrum further confirm the symmetrical arrangement of adamantyl group in
compounds IV and V.
References
1. I.V. Peterson, N.M. Svirskaya. A.A. Kondrasenko, A.I. Rubaylo. Magn. Reson. Chem. 2013, 51,
762–766.
This work was supported by Siberian branch of Russian academy of science (project of
multidisciplinary integration fundamental research № 18).
313
P203
DRAMATIC RECONSTRUCTION OF COBALT CATALYSTS DURING
FISCHER-TROPSCH SYNTHESIS: DRIVING FORCE AND MECHANISTIC
CONSEQUENCES
M. Saeys1, A. Banerjee2, K. Gunasooriya2
1 - Laboratory for Chemical Technology, Ghent University, Ghent, Belgium
2 - Department of Chemical and Biomolecular Engineering, National University of Singapore
The strong adsorption of reaction intermediates can introduce massive structural changes to the
surface of catalyst particles under reaction conditions [1,2] and often the catalytically active sites
form only under reaction conditions. Fischer-Tropsch synthesis converts synthesis gas, a mixture of
CO and H2, to long-chain hydrocarbons and water over supported cobalt catalysts. Under high CO
pressures, cobalt single crystals are found to undergo a massive reconstruction, leading to the
spontaneous formation of sub-2-nm cobalt islands, together with the formation of defect sites as
observed by DRIFT spectroscopy. [2] The driving force for this reconstruction and its kinetic
consequences remain poorly understood. Using Density Functional Theory with the RPBE-VdW
functional, we show that the unusual stability of square planar-carbon at the B5 step edges [3], as
well as the attractive interaction between this square-planar carbon and CO at the neighboring edge
site lead to a negative edge creation energy under reaction conditions, driving the formation of
nano-scale islands of well-defined shapes (Figure). Bonding analysis based on both Bloch states
and Natural Bond Orbitals elucidates the electronic origin for the exceptional stability of these
structures. The island sites created under reaction conditions are not fully covered during the FT
reaction and the available vacancies provide active sites for rapid CO activation, the initiation step
in the FT reaction mechanism [4].
Model for the nano-islands formed under Fischer-Tropsch conditions. The active sites, highlighted
in green, are created by the formation of the nano-islands.
References
[1] Tao, Dag, Wang, Liu, Butcher, Bluhm, Salmeron, Somorjai, Science, 3275967: 850 (2010);
Hansen, Wagner, Helveg, Rostrup-Nielsen, Clausen,Topsøe, Science, 2955562, 2053 (2002)
[2] Wilson, de Groot, J. Phys. Chem., 99, 7860, (1995)
[3] Alexandrova, Trinh, Saeys, submitted
[4] Zhuo, Borgna, Saeys, J Catal 297, 217, (2013)
314
P204
UNIQUE ROLE OF THE MULTI-LABILITY OF POLYDENTATE LIGANDS
FOR PD-CATALYZED C-O AND C-S CROSS COUPLING REACTIONS:
NEW REACTION PATHWAYS AND CATALYTIC RESTING STATES
M. Saeys1, N. Wijaya2, J.-C. Hierso3
1 - Laboratory for Chemical Technology, Ghent University, Ghent, Belgium
2 - 1Chemical and Pharmaceutical Engineering, Singapore-MIT Alliance, National University of
Singapore, Singapore
3 - Institut de Chimie Moleculaire, Universite de Bourgogne, Dijon, France
Versatile and robust tridentate ferrocenylphosphanes exhibit remarkable potential as supporting
ligands for Pd-catalyzed C-O coupling reactions. [1] The air-stable Pd-triphosphane system
performed efficiently for the selective heteroaryl ether synthesis for catalyst loadings as low as 0.2
mol% by opening a reaction path through an unusual penta-coordinated transition state (TS) as
demonstrated by DFT calculations (Figure). Natural Bond Orbital analysis shows that the stability
of the transition state originates from a 3-center-4-electron bond between the P lone pair, the Pd
center and a low-lying acceptor orbital on the substrate. Only for constrained polyphosphane
ligands, this gain in TS stability is not overwhelmed by an entropy penalty. [2] DFT calculations
further indicate that a similar penta-coordinated reaction path should facilitate C-S cross-coupling
reactions. [3] Unfortunately, constrained tridentate ferrocenylphosphanes perform poorly for this
cross-coupling reaction. Mechanistic studies using DFT show that the stability of the catalytic
resting states [4] cause this surprisingly different outcome. In C-S cross-coupling reactions, the
strong Pd-S bond stabilizes the resting states and a penta-coordinated reaction path does not
facilitate escape from those stable resting states. The stability of the resting states suggests that
ligands with a larger bite angle, and hence faster reductive elimination, should help the catalyst
system re-enter the catalytic cycle. Both theory and experiment show that a tetradentate binuclear
Pd catalyst therefore displays the highest activity, offering an optimal balance between enthalpy
gain and entropy penalty. Independent synthesis of the resting states for the variopus ligands also
confirms the relative reactivity predicted by theory.
tB u
Fe
P P h2
3 .2 5 Å
P Ph2
O Ar
Pd
P Ph2
tB u
R . E.
II
2 .6 3 Å
Pd
Fe
II
P ( i-P r) 2
H e tA r
P d ( II) in te r m e d ia te
tB u
- H e tA r O A r
tB u
tB u
PP h2
O Ar
P Ph2
PP h2
Fe
Pd
0
tB u
P (i-P r) 2
H e tA r
T r a n s itio n s t a t e
P ( i- P r ) 2
P d ( 0 ) in te r m e d ia te
C-O reductive elimination through a unique penta-coordinated transition state lowers the activation
free energy barrier by 10 kJ/mol and increased the catalytic activity by two orders of magnitude.
References
[1] Platon, Cui, Mom, Richard, Saeys, Hierso, Adv. Syn. Cat., 353, 3403, 2011.
[2] Wijaya, Cui, Platon, Hierso, Saeys, in preparation
[3] Platon, Wijaya, Rampazi, Cui, Rousselin, Saeys, Hierso, submitted
[4] Alvaro, Hartwig, J. Am. Chem. Soc., 2009, 131, 7858.
315
P205
THEORETICAL AND EXPERIMENTAL STUDIES PROCESSES
OLIGOMERIZATION AND ALKYLATION C6-C12 α-OLEFINS IN THE
PRESENT IONIC–LIQUID CATALYTIC SYSTEMS
Kh. H. Seidova, A.H. Azizov, R.V. Aliyeva, A.M. Abdullayeva
The Institute of Petrochemical Processes of the Azerbaijan National Academy of Sciences
In recent years, ionic liquids (ILs) are of great interest in the area of oligomerization and alkylation
processes. ILs have several benefits (low melting point, low volatility, reusability), including a lot
of good dissolved metal complexes. These properties are perfect for two-phase catalysis.
We carried out work on the oligomerization of C6-C12 α-olefins in the presence chloraluminate
ionic liquids based on AlCl3 and various amine hydrochlorides (triethylamine hydrochloride,
dietilamin hydrochloride, pyridine hydrochloride). In ILs were dissolved Ti-containing complexes
which is prepared by reacting TiCl4 and sterically hindered aminophenоl. In the presence of these
ILs catalytic systems derived oligoalkylnaphtenic oil (Mw=1300-4115, Mn=1435-5800, Mw/Mn =,
IV=124-162), not requiring hydrogenation step (since they do not contain double bonds in the
composition). Kinetic regularities (reaction order, activation energy, etc.) were installed on the basis
of experimental and theoretical data.
We have also carried out work on oligoalkylation toluene decene-1 in the presence of IL catalytic
systems. Obtained products were analyzed using chromatograph methods IR-, NMR-, UV-, and
DSC. It was established that they had Mw = 383-950, Mn =327-730, Mw / Mn = 1,17-1,3, IV = 88110.
Thus, in the presence of IL catalytic systems it is possible to obtain oligoalkylaromatic and
oligomeric products which can be used as synthetic lubricants for various applications.
316
P206
QUANTUM SIMULATION OF THE REACTION MECHANISM OF
ORGANOCATALYSES
C.H. Yu
National Tsing Hua University, Department of Chemistry, Hsinchu, Taiwan
Organocatalysis has received remarkable attraction recently. For instances, organic molecules have
been widely used as catalysts in the asymmetric synthesis of natural products. The reaction
mechanism of many chemical reactions of this type are too complicated to be tackled efficiently by
traditional optimization methods of quantum chemistry. The idea of incorporating the chemical
nature of the reaction into the search algorithm results in the constrained reduced-dimensionality
(CRD) algorithm.1
The CRD algorithm constructs the search path stepwise from linear combinations of a small set of
manually chosen coordinates (predictors). The rest, and majority, of the coordinates (correctors)
are optimized at every step of the search path to minimize the total energy such that the search path
becomes a minimum energy path connecting transition states and the desired products starting from
the reactants. Dynamic constraints, which are automatically activated and later revoked depending
on the state of some particular coordinates among the predictors, are quite often required to guide
the search of reaction path.
Practical applications of the constrained CRD algorithm to the study of stereoselective
organocatalysis successfully reveal the catalytic mechanism of the phosphine and amine catalyzed
reactions of the cycloaddition of allenoates and enones; and the nornicotine catalyzed Mannich
reaction. The cycloaddition of allenoates and enones yields [3+2] cyclopentenes in phosphine
catalysis, and [2+4] dihydropyrans or pyrans in amine catalysis.2 The quantum calculation not only
explains the different reactivity of the two types of catalysts but also reveals a new path to the α[2+4] product via an intermediate Rauhut-Currier reaction in amine catalysis. In the latter system,
the computations show that nornicotine can catalyze the intermolecular Mannich reaction in wet
solvents and water. The significant catalytic effect is owing to the elimination of the bottleneck of
the enol-formation step. In addition to the two examples, the constrained CRD algorithm has been
applied in many other complex reactions.
1. T. Lankau, C. H. Yu, J. Chem. Phys. 138 (2013) 214102; doi: 10.1063/1.4807743.
2. G. T. Huang, T. Lankau, and C. H. Yu, J. Org. Chem., 79, 1700-1711, 2014; doi:
10.1021/jo402609v.
317
P207
NEW DENTAL POLYMERIC MATERIALS REINFORCED WITH CARBON
NANOTUBES
I.V. Zaporotskova, L.S. Elbakyan
Volgograd state university, Institute of priority technologies, Volgograd, Russia
Fast curing plastics are widely used in dentistry clinic for relocation (to repair) prostheses, fix
dentures, orthodontic apparatus manufacture (Kapp, tyres), temporary prostheses, individual
impression spoons. A strong place occupy fast curing plastics are also among filling materials [1].
In connection with the above, the purpose of this study was to create a new materials (polymer) on
the basis of fast-hardening plastic «Carbodent».
In the experimental part of the work had been conducted selection of optimal conditions for
establishment of reinforced polymer nanotubes based on Carbodent: calculations and experiments
on definition of the optimal concentration of carbon nanotubes to create a composite. For this we
have prepared a series of samples with different percentages of the CNT and without carbon
nanotubes [2]. These samples were subjected to the test on firmness. Then the results were
compared.
Under the hardness understand the material's ability to resist impacts other phone
In the experimental part, in addition to the main investigated material «Carbodent», also studied
such dental materials, as «SNAP» (prod in USA) and dental cement (prod in Russia).
80
70
hardness BRIX
60
50
40
30
20
10
0
0
0,01
0,02
0,03
0,04
0,05
0,06
different percentages of carbon nanotubes
Fig1. Еhe dependence of the hardness values of the samples (carbodent) with different percentages
of carbon nanotubes
To prove the possibility of the implementation of the proposed mechanism, were performed
MNDO-calculations of the process of interaction of the basic polymer components carbodent
(methyl methacrylate, buthyl methacrylate, methacrylic acid) and carbon nanotubes. Molecules
were a step-close to the center of the CNT perpendicular to its surface, using one of the active
centers of the molecule.
Studies have shown the possibility of creating high-strength plastic polymer nanocomposites based
dental material «Carbogen" doped carbon nanotubes that can be used effectively not only in the
practice of orthodontics, but in subsectimeoriginal practices to create high strength of seals.
These polymeric materials are useful for creating dentures, orthodontic apparatus manufacture,
temporary prostheses, individual impression spoons, where the strength characteristics of the
material is much more important compared with the disadvantages color characteristics.
1. Brel A.K., Dmitrienko S.V., Kotlyarevskogo O.O.. Polymer materials in clinical dentistry. - Volgograd:
OOO«Blank»,2006.
2. Zaporotskova I.V.. Carbon and non-carbon nanomaterials and composite structures based on them: structure and
electronic properties. - Volgograd. 2009, 490 p.
318
P208
MONOMETALLIC AND BIMETALLIC GOLD-BASED CATALYSTS FOR
SELECTIVE OXIDATION OF GLUCOSE TO GLUCONIC ACID
V.I. Bukhtiyarov, O.P. Taran, B.L. Moroz, P.A. Pyrjaev, I.P. Prosvirin, I.V. Delidovich, N.V.
Gromov, V.N. Parmon
Boreskov Institute of Catalysis, Lavrentieva ave. 5, Novosibirsk 630090, Russia
At present, gluconic acid and its salts, which are widely used in the food, pharmaceutical, paper and
concrete industries, are manufactured by enzymatic oxidation of glucose or glucose-containing raw
materials. The biotechnological processes, however, may have serious economic and environmental
disadvantages. Replacing the enzymes as catalysts for glucose oxidation by a supported noble metal
catalysts is an attractive solution to the problem. However, the main benefit in application of
supported metal catalysts in organic synthesis, which consists in their easy separation from reaction
mixture containing reagents, reaction products and solvents, goes down by the worse selectivity
towards a target product. In our case, selectivity to the gluconic acid is decreased by a side reaction
of isomerization of glucose to fructose homogeneously catalyzed by hydroxyl-groups in solution
(pH in reactor was 8.8-9.2). Thus, increase in activity of heterogeneous catalysts will directly
enhance the selectivity to gluconic acid.
There are two principally different approaches to solve the problem which, however, supplement
each other: i) narrowing the particle size distribution around optimal size, and ii) introduction of the
second metal which will tune the electronic properties (ligand effect) or structure (ensemble effect)
of catalytically active sites. To demonstrate the efficiency of this approach we develop the
procedure for synthesis of monometallic (Au) and bimetallic (Pd-Au) nanoparticles supported on
alumina and on carbon (Sibunit) for testing their catalytic properties in liquid phase selective
oxidation of glucose with oxygen.
Investigation of preparation of the gold particles shows the size of alumina-supported gold
nanoparticles to be controlled via epitaxial interaction of gold with the support, with both
deposition-precipitation and anionic adsorption being applied as preparation method. In the case of
Sibunit, only cationic adsorption from Au(NH3)4+ complexes provides the formation of nanosized
gold particles on carbon after subsequent calcination of the impregnated catalyst. These catalysts
exhibit the size effects when the high TOF values are observed for gold particles with <d> from 1 to
5 nm, while increasing the mean particle size over 5 nm decreases activity.
The Au/support matrixes were applied for preparation of Pd-Au alloy particles via their
impregnation with palladium nitrate. Subsequent calcination at optimal temperature (230oC) and
optimal palladium content (Pd/Au atomic ratio of 1:4) results in formation of alloy nanoparticles
with preferable formation of Pd-Pd and Au-Au bonds compared to Pd-Au bonds. This structure of
the surface of alloy particles provides increasing the rate of selective oxidation of glucose via
concerted mechanisms where O2 molecule activates on Pd sites, and glucose acid on Au ones.
Accelerating the rate of the target reaction increases the selectivity to gluconic acid because the
catalysts do not affect the rate of the side reaction (isomerization of glucose catalyzed by OH- ions).
Variation of palladium content and temperature of calcination allowed us to reach commercially
attractive levels of selectivity to gluconic acid (95% for Pd-Au/Sibunit and 97% for Pd-Au/Al2O3
catalysts). The reasons of synergetic effects are discussed in terms of surface composition of
alloyed particles.
The work was supported President of Russian Federation for government support of Leading
Scientific Schools (grant SS-5340.2014.3) and RFBR (project 13-03-01003).
319
P209
[3+2] CYCLOADDITION-CYCLOREVERSION CASCADE OF THE
AZOMETHINE IMINES IN THE SYNTHESIS OF PYRAZOLE
DERIVATIVES
M.I. Pleshchev , N.N. Makhova
N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia
The general concept of the 1,3-dipolar cycloadditions was recognized by Huisgen in the early
1960’s. Later numerous examples of the reverse [3+2] cycloaddition reactions have been found,
which can be described as a cascade of dipolar cycloaddition – cycloreverion. Over the last few
years our group has been involved in the research of the reactivity of azomethine imines 1
catalytically generated in situ (BF3·OEt2 catalysis) from 6-aryl-1,5-diazabicyclo[3.1.0]hexanes 2.
We found three new reactions1-3 of cycloaddition – cycloreversion cascade of the azomethine
imines 1 under the action of aromatic aldehydes, aromatic and heteroaromatic ylidene
malononitriles or isatins resulting in the formation of new azomethine imines 3. The latter were
reacted in situ with a series of dipolarophiles giving fused heterocyclic systems with pyrazolidine
cycle annelated to pyrazolidine, pyrazole or thiadiazole cycles containing reactive functionalities or
pharmacophoric heterocyclic fragments (pyrrole, thiophene, indole).
1. V. Yu. Petukhova, M. I. Pleshchev, L. L. Fershtat, V. V. Kuznetsov, V. V. Kachala, and N. N. Makhova,
Mendeleev Commun., 22, 32 (2012).
2. M. I. Pleshchev, V. Yu. Petukhova, V. V. Kuznetsov, D. V. Khakimov, T. S. Pivina, M. I. Struchkova,
Yu. V. Nelyubina, and N. N. Makhova, Mendeleev Commun., 23, 34 (2013).
3. M. I. Pleshchev, V. Yu. Petukhova, V. V. Kuznetsov, D. V. Khakimov, T. S. Pivina, Yu. V. Nelyubina,
and N. N. Makhova. Russ. Chem. Bull., Int. Ed., 62, 1066 (2013).
320
P210
PHYSICOCHEMICAL AND CATALYTIC PROPERTIES OF NICKEL
PHOSPHIDE CATALYSTS: THE EFFECT OF PREPARATION AND
PRETREATMENT METHODS
I.V. Deliy1, I.V. Shamanaev1, E.Yu. Geresimo2, R.I. Kvon3, V.A. Rogov4, G.A. Bukhtiyarova3
1 - Boreskov Institute of Catalysis; Novosibirsk State University; Research and Educational Center
for Energoefficient Catalysis in Novosibirsk State University, Novosibirsk, Russia
2 - Boreskov Institute of Catalysis; Research and Educational Center for Energoefficient Catalysis
in Novosibirsk State University, Novosibirsk, Russia
3 - Boreskov Institute of Catalysis, Novosibirsk, Russia
4 - Boreskov Institute of Catalysis; Novosibirsk State University, Novosibirsk, Russia
Transition metal phosphides are considered as the promising systems for the hydrodeoxygenation
(HDO) of oxygen-containing compounds from renewable feedstocks. The peculiarities of metal
phosphides systems are the low stability in the air and a requirement of rereduction before reactions.
Therefore, catalytic properties of the phosphide systems could be dependent on the conditions of
their preparation and rereduction. The aim of the present work is to investigate the influence of
preparation parameters on the formation of NixPy phase and the catalytic activity of silica-supported
nickel phosphide catalysts in hydrodeoxygenation of methyl palmitate as the representative model
components of triglyceride-based feedstock.
A series of silica-supported nickel phosphide catalysts were prepared by means of temperatureprogrammed reduction (TPR) of the nickel phosphates (A) or nickel phosphite (I) precursors, with
varying Ni/P molar ratios followed by reduction in H2 The catalysts were characterized by
elemental analysis, N2 physisorption, XRD, H2-TPR, HRTEM and XPS.
To examine the influence of preparation and reactivation parameters a series of silica-supported
nickel phosphide catalysts were prepared. According to H2-TPR analysis the Ni/P molar ratio equal
to 2/1 on the impregnation step leads to the sequental reduction of nickel oxide at low temperature
and the formation nickel phosphide at high temperature, whereas 1/1 or 1/2 molar ratios result to the
reduction of oxide precursors only at high temperature. XRD analysis of the reduced catalysts
confirmed the presence of Ni12P5 phase on the surface of the SiO2 for sample with Ni/P=2/1 from
(A) series and the presence of Ni2P phase for catalysts with Ni/P=1/2 and 1/1 from (A) and (I)
series. The HR-TEM data revealed the larger mean particles sizes in the samples from (I) series
(10-30 nm) than in the samples from (A) series (5-10 nm).
It was observed that two parallel reaction pathways occur during the methyl palmitate
transformation over Ni phosphide catalysts: decarbonylation through СО and С15 hydrocarbons
formation and hydrodeoxygenation through H2O and С16 hydrocarbons formation. The increasing
the phosphorous content in the catalyst rises the catalytic activity in the methyl palmitate
hydrodeoxygenation, but selectivity towards the С16 hydrocarbons remains the constant for each (A)
or (I) series. The catalysts prepared by (I) method were the most active and selective toward to C16
hydrocarbons. It was shown for the phosphate type precursors from (A) series may be applied the
method of the reduction at low temperature in-situ the reactor without declining the catalytic
activity. On the basis of the obtained results the optimal preparation and reactivation conditions for
silica-supported nickel phosphide catalysts were proposed.
Acknowledgements - The work was performed with support of the Skolkovo Foundation (Grant
Agreement for Russian educational organization №1 on 28.11.2013).
321
P211
SELECTIVE HYDROGENATION OF NITROAROMATIC COMPOUNDS
OVER SUPPORTED Au/Al2O3 CATALYST IN A CONTINUOUS-FLOW
REACTOR
A.L. Nuzhdin1, B.L. Moroz2, S.I. Reshetnikov1, P.A. Pyrjaev1, G.A. Bukhtiyarova1, V.I.
Bukhtiyarov2
1 - Boreskov Institute of Catalysis, Novosibirsk, Russia
2 - Boreskov Institute of Catalysis; Novosibirsk State University, Novosibirsk, Russia
Functionalized anilines are an important class of industrial intermediates for a variety of specific
and fine chemicals, including pharmaceuticals, dyes, herbicides and pesticides. Industrial process of
anilines production via reduction of nitrobenzenes using Fe/HCl reducing system (Bechamp
reaction) is no longer viable due to the generation of significant amounts of toxic waste. Liquid
phase catalytic hydrogenation is a “green” alternative to the Bechamp process. Supported gold
catalysts (Au/TiO2, Au/Al2O3, Au/Fe2O3) provide the liquid-phase reduction of nitrobenzenes to
corresponding anilines with high chemoselectivity, as it was shown during the experiments in batch
reactors [1]. Meanwhile, continuous flow processes are more efficient than standard batch protocols
and offer much higher throughput, better control of process variables and less waste levels [2].
Herein, we present the results of the study on the selective nitro group hydrogenation in nitroarenes
containing halogens, C=C or C=O bonds over the nanosized Au/Al2O3 catalyst under continuousflow conditions.
The 2.0% Au/Al2O3 catalyst with a mean diameter of Au particles equal to 1.8 nm was prepared by
”deposition-precipitation” technique. The catalytic activity was tested using the H-Cube Pro
instrument equipped with a continuous-flow reactor at 60-110 ºC and 10 bars of H2. A 0.05 M
solution of nitroaromatic compound (3-nitrostyrene, 4-nitroacetophenone, 2-, 3- or 4chloronitrobenzenes) in toluene containing n-decane (0.5 vol. %) as internal standard was fed into
the reactor at the flow rate of 0.5 mLmin-1 and mixed with H2 supplied through the catalyst bed at
the rates of 8.4-60 mLmin-1. The reaction products were analyzed by GC and GC-MS.
As one of the important results, we found that hydrogenation of chloronitrobenzenes over the
Au/Al2O3 catalyst under continuous-flow conditions gives the corresponding chloroanilines with
almost 100% yield, formation of any dechlorination products being not detected at all. Increasing
the reaction temperature suppresses the intermediate formation of nitroso compounds and
condensation products. Hydrogenation of 3-nitrostyrene and 4-nitroacetophenone carried out in a
flow reaction under optimal conditions leads to the formation of corresponding anilines with 91%
and 97 % yields, respectively, at much lower temperatures than those usually used in the batch
reactors. Rising the reaction temperature favors hydrogenation of C=C and C=O bonds to the
detriment of selectivity on the target anilines. This work demonstrates for the first time, that the
Au/Al2O3 catalyst provides hydrogenation of various nitrobenzenes containing chlorine, C=С or
С=O bonds to corresponding anilines in a continuous-flow reactor with a high activity and
selectivity under determined conditions such as reaction temperature, H2 pressure and flow rate.
Financial support has been provided by grant of RFBR (grant 13-03-12178) and grant of President
of Russian Federation for government support of Leading Scientific Schools (grant SS5340.2014.3).
1. P. Serna, M. Boronat, A. Corma, Top Catal. 54, 439 (2011).
2. M. Irfan, T. N. Glasnov, C. O. Kappe, ChemSusChem. 4, 300 (2011).
322
P212
A COMBINED KINETIC AND DFT STUDY ON THE MECHANISM OF
THIOETHER SULFOXIDATION WITH HYDROGEN PEROXIDE
CATALYZED BY A DIMERIC POLYOXOMETALATE
[( -SiW10TI2O38H2)2O2]8I.Y. Skobelev1, O.V. Zalomaeva1, G.I. Maksimov1, J.J. Carbo2, J.M. Poblet 2, O.A. Kholdeeva1
1 - Boreskov Institute of Catalysis SB RAS, 630090, pr. Lavrentieva 5, Novosibirsk, Russia
2 - Department de Quimica Fisica i Inorganica, Universitat Rovira i Vigili, Marcel li Domingo s/n,
43007 Tarragona, Spain
The mechanism of methyl phenyl sulfide (PhSMe) oxidation with aqueous H2O2 mediated by a
Keggin-type polyoxometalate (POM), [( -SiW10Ti2O38H2)2O2]8- (Ti4-POM) [1], has been studied
using a combination of kinetic modeling and DFT calculations. The active oxidizing species forms
via interaction of H2O2 with the POM moiety, which can be either the initial dimeric Ti4-POM or
monomeric [( -SiW10Ti2O38H2)(OH)2]4- (Ti2-POM) generated through hydrolysis of Ti_O_Ti bonds
linking two Keggin polyanions in Ti4-POM. Therefore, two alternative mechanisms of sulfoxidation
were considered (Fig. 2, A and B).
Ti4-PОМ
-H2O
K1=k1/k-1
k1
Ti2-PОМ
H2O2
k-1
H2O2
k2
H2O
k-2
H2O
Ti4-PОМ
H2O2
H2O
H2O2
k4
PhS(O)Me
H2O
k3 PhSMe
k-4
H2O
PhS(O)Me
k5
PhSMe
Ti4-PОМ-OOH
Ti2-PОМ-OOH
B
A
Fig. 2. Alternative mechanisms for PhSMe sulfoxidation with H2O2 in the presence of Ti4-POM
A steady-state approximation was applied to derive rate laws for both mechanisms. Experimental
initial rates were fitted by both rate laws using a chi-square error function. According to the kinetic
modeling, mechanism A that involves the hydrolysis step dominates over mechanism B. The DFT
calculations on the sulfoxidation process also support this choice. The formation of a titanium
hydroperoxo complex is more favorable for Ti2-POM: the corresponding transition state is 6.5
kcal·mol-1 lower in energy relative to Ti4-POM. The activation barrier for oxygen atom transfer is
3.6 kcal·mol-1 lower for Ti2-POM relative to Ti4-POM. The activation barriers of the hydroperoxo
complex formation and oxygen atom transfer are very close to each other, so that there is no definite
rate-limiting step, which is in agreement with the kinetic data. Computed ΔG for the Ti4-POM
hydrolysis, hydroperoxide activation, and sulfoxidation steps are in good agreement with the
experimental estimations.
Acknowledgements. The research was partially supported by RFBR (grant No. 13-03-12042).
I.Y.S. acknowledges Polyoxometalate Chemistry for Molecular Nanoscience (PoCheMoN) action
in the framework of European Cooperation in Science and Technology (COST) program and
Universitat Rovira i Vigili for financial support.
[1] Goto Y., et al. Inorg. Chem. 2006, 45, 2347.
323
P213
THE IMMOBILIZED AND RECYCLE CATALYST FOR ASYMMETRIC
FRIEDEL-CRAFTS REACTION
V.G. Desyatkin, M.V. Anokhin, I.P. Beletskaya
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
In this work we obtained BOX-ligand 1, immobilized on the polymer matrix and tested catalytic
active of our catalyst.
As the polymer matrix, we chose commercially available Merrifield resin. The of BOX-ligand 1
immobilization on the polymer matrix was performed using the «click»-reaction. After the
treatment the polymer BOX-ligand 2 by copper (II) triflate catalyst 3 was obtained.
Polymeric catalyst 3 was used for asymmetric Friedel-Crafts reaction indoles and different Michael
acceptors (arylidenemalonates, arylidenepyruvate) and methyl 3,3,3-thrifluoropyruvate. Products of
reactions were obtained with high yields (up to 99%) and high enantiomeric excess (up to 99%).
The catalyst 3 was recycled of several times.
324
P214
SYNTHESIS OF 4H-PYRANO[2,3-D]PYRIDO[3',2':4,5]THIENO[3,2B]PYRIDINES BY COMBINATION OF DOMINO REACTIONS
N.A. Larionova, A.A. Zubarev, L.A. Rodinovskaya, I.V. Zavarzin, A.M. Shestopalov
N. D. Zelinsky institute of organic chemistry, Leninsky prospekt, 47, 119991 Moscow, Russia
The recyclization reaction of dithiacyclohexenes (1) to 3-cyanopyridine-2(1H)-thiones (2) has been
earlier developed1. Based on the study of the mechanism of this reaction 2 we developed a new,
convenient method for the synthesis of substituted pyridines (2) It represents the domino reaction
(Knoevenagel reaction → Michael reaction → hetero-Thorpe-Ziegler reaction) of aldehydes (3),
cyanothioacetamide (4) and cyclic ketones (5). The second domino reaction (SN2 reaction →
Thorpe-Ziegler reaction → Thorpe-Guareschi reaction) of 5,6-annulated 3-cyanopyridine-2(1H)thiones (2) and ethyl 4-chloroacetoacetate (6) result in dipyridothiophenes (7). The third domino
reaction (Knoevenagel reaction → Michael reaction → hetero-Thorpe-Ziegler reaction) of
dipyridothiophenes (7) with aromatic aldehydes and malononitrile result in fused pyranes 8. It is
known that fluorinated analogues of obtained compounds showed high anticancer activity.
The developed approach has been applied for the synthesis of androstenodipyridothiophene 9.
References:
1. Sharanin Y.A., Promonenkov V.K., Shestopalov A.M., Zh. Org. Khimii, 1982, vol. 18, p. 1782
[J. Org. Chem. USSR (Engl. Transl), 1982, vol. 18, p. 1557].
2. Shestopalov A. M., Rodinovskaya L. A., Shestopalov A. A. Recyclization reactions of
degenerated carbo- and heterocycles: practical retrosynthetic approach to new multicomponent
methods of synthesis of N-containing five and six member ring heterocycles. In “Nitrogencontaining heterocycles”. Ed. V. G. Kartsev, ICSPF Press, Moscow, 2006, Vol.1, p. 146.
325
Authors Index
326
327
Baikov S.V. .............................................................. 304
Bakhtin S.G. ............................................................. 251
Balagurova E.V. ....................................................... 282
Banerjee A. ............................................................... 313
Barachevsky V.A. .................................................... 185
Baral E.R. ................................................................. 121
Baranovsky A.V. ...................................................... 123
Barbier P................................................................... 250
Bastrakov M.A. ........................................................ 122
Bastrakova G.V. ....................................................... 222
Batkin A.M. ...................................................... 216, 266
Batyrshin N.N........................................................... 151
Baulin V.E. ............................................................... 278
Baumer M. ................................................................ 228
Beck I.E. ................................................................... 216
Bei M.P. ................................................................... 123
Beletskaya I.P. ... 20, 111, 118, 131, 165, 183, 209, 211,
250, 258, 260, 290, 309, 323
Belevtsev Ya.E. ........................................................ 248
Belkova N.V. ...................................................... 87, 265
Belov D.S. ........................................................ 140, 243
Belov G.P. ................................................................ 116
Belyaeva E.V. ........................................................... 277
Belykh L.B. .............................................................. 276
Belyy A.Yu. ............................................................. 124
Berestneva Yu.V. ..................................................... 242
Bessmertnykh-Lemeune A.G. .......................... 111, 211
Bityukov O.V. .......................................................... 285
Bokarev D.A..................................................... 125, 217
Bolm C. ...................................................................... 11
Bondarenko T.N. .............................................. 108, 146
Borovlev I.V. ............................................................ 126
Bouquillon S. ...................................................... 94, 208
Boyko I.I. ................................................................. 171
Bragina G.O. .................................................... 216, 266
Branco L.C. ........................................................ 95, 127
Bratskaya S.Yu. ........................................................ 288
Brel V.K. .................................................................. 249
Broehl A. .................................................................... 31
Bronstein L.M. ......................................................... 107
Bruk L.G. ................................................................. 232
Budynina E.M. ................................................... 72, 163
Bukhtiyarov V.I. ............... 216, 266, 267, 318, 319, 321
Bukhtiyarova G.A. ........................................... 320, 321
Bulich E.Yu. ............................................................. 199
Bunev A.S. ....................................................... 128, 129
Burangulova R.N. ..................................................... 114
Butenschoen H. .......................................................... 61
Butin A.V. ................................................................ 201
Buzin M.I. ................................................................ 248
Bykov E.E. ............................................................... 130
A
Abadie M.A................................................................ 97
Abdullayeva A.M. .................................................... 315
Abel A.S. .................................................................. 111
Abramov P.A. .......................................................... 101
Agafonov Yu.A. ....................................................... 112
Agbossou-Niedercorn F. .................................... 97, 113
Agliullina R.A. ......................................................... 203
Ahmedova R.Q. ....................................................... 306
Aisina K.E. ............................................................... 222
Akhmetov A.R. ........................................................ 105
Akita M. ..................................................................... 34
Aksenov A.V. ..................................................... 65, 115
Aksenov D.A.............................................................. 65
Aksenov N.A...................................................... 65, 115
Aksenov N.G. ........................................................... 114
Aksenova I.V. .................................................... 65, 115
Alabugin I.V. ............................................................. 23
Aleksandrov I.V. ...................................................... 287
Aleksanyan D.V. ...................................................... 104
Alexiou X. ................................................................ 227
Alferov K.A. ............................................................ 116
Aliyeva H.Sh. ........................................................... 205
Aliyeva R.V. .................................................... 310, 315
Allegro D. ................................................................ 250
Amangasieva G.A. ................................................... 126
Amao Y. ................................................................... 117
Ananev I.V. .............................................................. 279
Ananikov V.P. . 29, 63, 89, 90, 137, 149, 154, 165, 170,
173, 207, 229, 231, 234, 244, 252, 253, 263, 299
Andreev I.A...................................................... 140, 243
Andronati S.A. ......................................................... 233
Anisimov A.P. .......................................................... 175
Anisimova V.I. ......................................................... 151
Anokhin M.V. .......................................... 118, 309, 323
Antonova T.N. ......................................................... 283
Arbatsky N.P. ........................................................... 175
Argunov D.A. ............................................................. 96
Arkhipov D.E. .......................................................... 103
Arutyunyants A.A. ................................................... 308
Arzumanyan A.V. .................................................... 237
Asachenko A.F. .......................................................... 62
Astakhov A.V. ......................................................... 102
Averin A.D. .............................................. 111, 118, 131
Averina E.B...................................................... 119, 251
Ayyappan A. .............................................................. 71
Azizov A.H. ..................................................... 310, 315
Azov V.A. .................................................................. 85
Azpiroz R. .................................................................. 42
C
B
Cao Z.X. ..................................................................... 70
Capet F. ...................................................................... 97
Carbo J.J. .................................................................. 322
Carrera G. ................................................................. 127
Castarlenas R. ............................................................. 42
Cavallo L. ................................................................... 69
Chagarovskiy A.O. ..................................................... 72
Babayev E.R. ........................................................... 205
Babayeva F.A. .......................................................... 306
Badyrova N.M. ................................................. 120, 224
Baev A.K.................................................................. 307
Baev D.S. ................................................................. 172
Baeva G.N. ....................................................... 215, 217
328
Che C.-M.................................................................. 158
Chekunaev N.I. ........................................................ 168
Chen S.H. ................................................................... 93
Cheptsov D.A. .......................................................... 162
Cherepanova A.V. .................................................... 172
Chernenko A.Yu. ..................................................... 102
Chernichenko N.M. .................................................. 131
Chernoburova E.I. .................................................... 132
Chernyshev V.M. ..................................................... 102
Chernysheva N.B. .................................................... 254
Cherry L. .................................................................... 36
Chigorina E.A. ......................................................... 308
Chigorina T.M.......................................................... 308
Chilov G.G. .............................................. 133, 227, 299
Chizhevsky I.T. ........................................................ 282
Chizhov А.О. ........................................................... 280
Chudinova Y.V. ....................................................... 134
Chudov K.S. ............................................................. 185
Chusov D. .................................................................. 74
Chuvaeva I.V. .......................................................... 246
Chuvylkin N.D. ........................................................ 213
Combes S. ................................................................ 250
Cronk W.C. ................................................................ 28
Cuong H.T................................................................ 112
E
Edwards A. ................................................................. 73
Egorov M.P. ....................................................... 18, 284
Egorova E.V. ............................................................ 125
Egorova K.S. ............................................................ 253
Elbakyan L.S. ........................................................... 317
Elinson M.N. ............................................ 218, 245, 284
Eliseev O.L. ...................................... 108, 141, 142, 146
Enikeev A.R. ............................................................ 147
Enikeeva L.V. ........................................................... 148
Epishina M.A. .......................................................... 204
Epstein L.M. ............................................................... 87
Eremin D.B. ............................................................. 149
Evdokimova A.I. ...................................................... 102
Eyvazova I.M. .......................................................... 205
F
Faerman V.I. ............................................................. 250
Farzaliyev V.M......................................................... 205
Fateenkov V.N. ........................................................ 150
Fateenkova O.V. ....................................................... 150
Fedorov A. Yu. ........................................................... 54
Fedorov A.Yu. .......................................................... 250
Fedorova G.B. .......................................................... 280
Filatov A.V. .............................................................. 235
Filippov O.A............................................................... 87
Finkelshtein E.Sh. .................................................... 155
Fodran P. .................................................................. 274
Fogg D.E. ................................................................... 12
Fokin V.V. .......................................................... 27, 250
Fomenkov I.V........................................................... 303
Fujisawa J. .................................................................. 83
D
Da Ponte M.N. ......................................................... 127
Daineko S.I. ............................................................. 248
Dalinger I.L. ............................................................. 135
Danheiser R.L. ........................................................... 15
Davshan N.A. ........................................................... 136
Degtyareva E.S. ....................................................... 137
Delidovich I.V. ......................................................... 318
Deliy I.V. ................................................................. 320
Demchuk D.V. ......................................................... 254
Demidov O.P............................................................ 126
Denisova Yu.I. ......................................................... 155
Dernovaya E.S. ........................................................ 279
Desyatkin V.G. ................................................. 309, 323
Dey S........................................................................ 138
Di Giuseppe A. ........................................................... 42
Dilman A.D. ....................................... 50, 182, 196, 300
Direnko D.Yu. .......................................................... 139
Dobrokhotova Zh.V. ................................................ 181
Dokichev V.A. ................................................. 193, 287
Dolgushin F.M. ........................................................ 282
Dolotov S.M. ............................................................ 162
Dorokhov V.S. ......................................... 141, 142, 177
Drevko B.I................................................................ 139
Drevko Ya.B. ........................................................... 139
Dudinov A.A. ................................................... 188, 262
Duker M.H. ................................................................ 85
Dutov M.D. .............................................................. 222
Dyakonov V.A. ................................ 143, 167, 202, 203
Dzhafarov M.Kh ...................................................... 145
Dzhafarov M.Kh. ..................................................... 144
Dzhemilev U.M. ....................... 105, 143, 167, 202, 203
Dzhevakov P.B. ......................................................... 62
G
Gadirov A.A. ............................................................ 311
Gadzhiev O.B. .......................................................... 228
Gaidai N.A. .............................................................. 112
Gainulina E.T. .......................................................... 150
Garaeva G.T. ............................................................ 151
Gavrin S.S. ............................................................... 194
Gazizov M.B. ........................................................... 114
Gazizullina G.F. ....................................................... 167
Gelman D. .................................................................. 87
Gerbst A.G. ................................................................ 96
Geresimo E.Yu. ........................................................ 320
German K.E. ............................................................. 152
Gevorgyan V. ............................................................. 16
Giernoth R. ................................................................. 31
Giorgi G. .................................................................... 83
Gladkikh E.G. ........................................................... 280
Gladysz J.A. ............................................................... 17
Glazkova M.N. ......................................................... 152
Glazova I.A. ............................................................. 219
Golovanov I.S............................................................. 66
Golubev P.R. ............................................................ 153
Gordeev E.G. ...................................................... 90, 154
Gordeev V. Yu. ........................................................ 287
Goulioukina N.S. .............................. 211, 258, 260, 290
329
Grebennikov E.P. ..................................................... 185
Grela K.L. .................................................................. 57
Gribanov P.S. ............................................................. 62
Grigoriev M.S. ......................................................... 152
Gringolts M.L. ......................................................... 155
Grishina G.V. ............................................................. 81
Gromov N.V. ........................................................... 318
Grunert W. ............................................................... 277
Gubaidullin I.M. ....................................................... 147
Gubaydullin I.M. ...................................................... 148
Guilard R. ................................................................. 211
Guliev A.D. .............................................................. 310
Gulikova D.K. .......................................................... 150
Gunasooriya K. ........................................................ 313
Gusev D.G................................................................ 156
Gushchin A.L. .......................................................... 101
Guskov P.O. ..................................................... 246, 247
Kadikova G.N........................................................... 167
Kaledin V.A. ............................................................ 172
Kalinin R.G. ............................................................. 195
Kalsin A.M. .............................................................. 265
Kamenz B.L. ............................................................ 157
Kaplan A.M. ............................................................. 168
Kapustin G.K. ........................................................... 268
Kardash V.A. ............................................................ 195
Karelin A.A. ............................................................. 169
Kashin A.S. ...................................................... 170, 252
Katrukha G.S. ........................................................... 280
Kavun A.M. ...................................................... 199, 200
Kazimzadeh A.K. ..................................................... 311
Kempe R..................................................................... 19
Keshtov M.L............................................................. 184
Khachatryan D.S. ..................................................... 171
Khairullin R.A. ......................................................... 114
Khalilov L.M. ........................................................... 105
Khamiyev M.J. ......................................................... 310
Khanmetov A.A. ...................................................... 310
Khatashkeev A.V. .................................................... 224
Khatuntseva E.A. ...................................................... 172
Khemchyan L.L. ......................................... 90, 165, 244
Khlebnikov A.F. ......................................................... 91
Khokhlov A.R. ......................................................... 184
Khokhlova E.A. ........................................................ 173
Kholdeeva O.A. ........................................................ 322
Khrapkovskii G.M. ................................................... 223
Khudorozhkov A.K. ................................. 266, 267, 319
Khuzin A.A. ............................................................. 105
Kim D. -S. .................................................................. 67
Kim D.-S. ................................................................. 174
Kirillov E. ................................................................... 75
Kirsheva N.A. ........................................................... 175
Kiryanov I.I. ............................................................. 105
Kiselyova A.V. ......................................................... 195
Kitaura K. ................................................................... 88
Klyba L.V. ........................................................ 160, 161
Knirel Y.A. ....................................... 175, 235, 255, 297
Knyazeva E.A........................................................... 241
Kobeleva O.I. ........................................................... 185
Kochurov V.S. .......................................................... 184
Kofanov E.R. ............................................................ 304
Kogan V.M. ...................... 141, 142, 176, 177, 178, 179
Koike T....................................................................... 34
Kolesnikov G.V. ....................................................... 152
Kolesnikov P.N. ......................................................... 74
Kolotova E.S. ........................................................... 227
Komarova B.S. ......................................................... 180
Komogorttsev A.N. .......................................... 188, 262
Kondakova A.N. ....................................................... 175
Kondrasenko A.A. .................................................... 312
Konev A.S. ................................................................. 91
Konstantinov I.O. ............................................. 184, 195
Konstantinova L.S. ................................................... 241
Konyushkin L.D. .............................................. 249, 254
Koptyug I.V. ............................................................... 39
Kormanov A.V. ........................................................ 135
Koroteev P.S............................................................. 181
Kosobokov M.D. ........................................ 50, 182, 196
Kostyukovich A.Yu. ................................................. 282
Kotovshchikov Y.N. ................................................. 183
Kozitsyna N.Yu. ......................................................... 80
H
Hasegawa J.H. ............................................................ 78
Hashmi A.S.K. ........................................................... 10
Hayes P.G. ............................................................... 157
He H.-T. ................................................................... 240
Hierso J.-C. .............................................................. 314
Huang J.-S. ............................................................... 158
I
Ibragimov X.D. ........................................................ 306
Ignatov S.K. ..................................................... 219, 228
Ikeyama S................................................................. 117
Ilyukhin A.B. ........................................................... 181
Incerti-Pradillos C.A. ................................................. 48
Inozemtseva O.V. ............................................. 160, 161
Ioffe S.L. ............................................................ 66, 103
Irle S. .......................................................................... 76
Isaeva V.I. ........................................................ 268, 277
Ishii A. ....................................................................... 49
Ishitani O. ................................................................... 24
Ivanov I.V. ............................................................... 162
Ivanov K.L. .............................................................. 163
Ivanov S.A. .............................................................. 175
Ivanova I.K. ............................................................. 164
Ivanova I.S. .............................................................. 278
Ivanova J.V. ............................................................. 165
Ivanova O.A. ...................................................... 72, 163
J
Janssens P................................................................... 64
Jiang H.-F. .................. 92, 166, 239, 240, 292, 293, 301
Johnson K.R.D. ........................................................ 157
Jun C. -H. ................................................................... 67
Jun C.-H. .......................................................... 174, 264
K
Kabeshov M.A. .......................................................... 48
Kachala V.V. ............................................ 173, 200, 253
330
Kozlov V.A. ............................................................. 104
Kravtsov V.Ch. ........................................................ 233
Krayushkin M.M. .... 132, 184, 185, 186, 187, 188, 199,
200, 262, 295
Krentsel L.B. ............................................................ 155
Krukovskaya N.V..................................................... 144
Krylov I.B. ....................................................... 189, 294
Krylov K.S. .............................................................. 188
Krylov V.B. ........................................................ 96, 286
Krylova I.V. ............................................................. 284
Kryshtal G.V. ........................................................... 269
Kryuchkova E.V. ..................................................... 190
Kryzhovets O.S. ....................................................... 152
Kucherenko A.S. ...................................... 190, 198, 269
Kuchurov I.V. .......................................... 190, 281, 303
Kudryavtsev Ya.V. ................................................... 155
Kuklin S.A. .............................................................. 184
Kulakova A.N. ................................................. 191, 298
Kulakovskaya E.V. .................................................. 172
Kulakovskaya T.V. .................................................. 172
Kulikov A.S. ............................................................ 204
Kulyaeva V.V. ......................................................... 280
Kumar N.N.B. ............................................................ 28
Kunz S...................................................................... 228
Kurbatova E.A. ................................................ 270, 271
Kurek D.V. ............................................................... 134
Kurkin A.V. ............................................. 140, 192, 243
Kurnosov N.M. ........................................................ 106
Kustov A.L. .............................................................. 136
Kustov L.M. ............................................. 136, 268, 277
Kutateladze A.G. ........................................................ 28
Kuznetsov M.A. ................................................. 99, 230
Kuznetsova T.S. ............................................... 119, 251
Kvon R.I. .................................................................. 320
Liu C......................................................................... 159
Liu H.B. .................................................................... 159
Loc L.C. ................................................................... 112
Lukashev N.V........................................................... 183
Lukyanenko E.R. ...................................................... 192
Luzyanin K.V. .................................................... 63, 207
Lvov A.G. ......................................................... 199, 200
M
MacMillan D.W.C. .......................................................9
Maj A.M. .................................................................. 113
Makarov A.A. ................................................... 143, 202
Makarov A.S. ........................................................... 201
Makarova E.Kh. ....................................................... 202
Makarova M.O. ........................................................ 280
Makhaev V.D. .......................................................... 116
Makhamatkhanova A.L. ........................................... 203
Makhova N.N. .......................................................... 204
Maksimov G.I........................................................... 322
Makukhin N.N. ......................................................... 260
Maleev V.I. ................................................................. 74
Maleeva M.A. ........................................................... 147
Malkov A.V. ............................................................... 48
Mammadova P.Sh. ................................................... 205
Mammadova R.A. .................................................... 311
Manin A.N. ............................................................... 206
Marjanov A.S. .................................................... 63, 207
Markov P.V. ..................................................... 267, 268
Mashkovsky I.S. ......................................... 80, 267, 268
Maslakov K.I. ........................................................... 179
Masunov A.E. ........................................................... 228
Matevosyan K.R. ...................................................... 171
Matveeva V.G. ......................................................... 107
Medina F. ................................................................... 97
Medved’ko A.............................................................. 98
Men’shov V.M. ........................................................ 172
Menot B. ............................................................. 94, 208
Mereshchenko A.S. .................................................... 91
Michon C. ................................................................... 97
Mikhalitsyna E.A. .................................................... 209
Mikhaylov A.A......................................................... 103
Minaev P.P. .............................................................. 178
Minina N.E. .............................................................. 194
Mironovich L.M. ...................................................... 210
Miroshnikov K.A. .................................................... 255
Mitchenko S.A. .......................................................... 52
Mitrofanov A.Y. ....................................................... 290
Mitrofanov A.Yu. ..................................................... 211
Miyahara T. ................................................................ 82
Mochalova A.E......................................................... 219
Mokhov V.M. ........................................................... 221
Molchanova M.S. ..................................................... 247
Monnier F. .................................................................. 30
Moran W.J. ............................................................... 212
Morokuma K. ............................................................. 36
Moroz B.L. ....................................................... 318, 321
Morozov O.S. ............................................................. 62
Morozov V.A. .......................................................... 213
Mozhaev A.A. .......................................................... 178
Mozhaev A.V. .......................................................... 179
Mukhina O.A. ............................................................. 28
L
Laktionov P.P. .......................................................... 172
Lapchinskaya O.A. ................................................... 280
Lapidus A.L. .................................... 108, 112, 141, 146
Larichev Yu.V. ......................................................... 216
Larionova N.A. ................................................ 305, 324
Latypova D.R. .......................................................... 193
Latyshev G.V. .......................................................... 183
Lebedeva M.V.......................................................... 194
Lee Y.R. ........................................................... 121, 238
Lenev D.A. ............................................................... 195
Letarov A.V. ............................................................ 297
Levchenko K.S. ................................................ 185, 186
Levin O.V. ................................................................. 91
Levin V.V. ......................................... 50, 182, 196, 300
Li J.-X. ....................................................................... 92
Li X.-W. ................................................................... 166
Li Y.L......................................................................... 93
Lichitsky B.V. .................................................. 188, 262
Liebeskind L.S. .......................................................... 25
Lin Z. ....................................................................... 120
Lindale M.G. .............................................................. 25
Lingscheid Y. ............................................................. 31
Lipkind M.B. ............................................ 197, 226, 289
Lisnyak V.G. ............................................................ 198
Litmanovich A.D. .................................................... 155
331
Mulina O.M.............................................................. 214
Murzasheva N.F. ...................................................... 148
Musa S. ...................................................................... 87
Musaev D. .................................................................. 37
Myannik K.A. .......................................................... 186
Myasnyanko I.N. ...................................................... 192
Myshenkova T.N...................................................... 146
Mytareva A.I. ................................................... 215, 217
P
Palacios L. .................................................................. 42
Panchenko S.P. ......................................................... 118
Pankova A.S. .............................................. 99, 153, 230
Panova Y.S. .............................................................. 231
Panteleeva E.V. ........................................................ 236
Park H. -S. .................................................................. 67
Parmon V.N. ............................................................. 318
Pastukhova Z.Y. ....................................................... 232
Pavlovsky V.I. .......................................................... 233
Peganova T.A. .......................................................... 265
Peng S.M. ................................................................... 14
Pentsak E.O. ............................................................. 234
Perepelov A.V. ......................................................... 235
Perez-Torrente J.J. ...................................................... 42
Perlovich G.L. .................................................. 206, 273
Permyakov E.A. ....................................................... 142
Peshkov R.Yu. .......................................................... 236
Peterson I.V. ............................................................. 312
Petrova L.A. ............................................................. 116
Pimerzin A.A. ................................................... 178, 179
Pisareva I.V. ............................................................. 282
Poater A. ..................................................................... 69
Poblet J.M. .............................................................. 322
Podgorsky V.V. ........................................................ 279
Podmareva O.N. ....................................................... 279
Podolnikova A.Y. ..................................................... 210
Podyacheva E.S. ....................................................... 209
Pogozheva V.V......................................................... 280
Polo V......................................................................... 42
Polyakova I.N. .......................................................... 278
Polynski M.V. ............................................................ 89
Ponomareva E.A. ...................................................... 125
Popkov S.V. ............................................................. 222
Popov Yu.V. ............................................................. 221
Popova A.V. ............................................................. 255
Popova N.A. ............................................................. 172
Portnyagin A.P. ........................................................ 288
Pototskiy R.A. .................................................. 237, 298
Poudel T.N. .............................................................. 238
Povolotskiy A.V. ........................................................ 91
Preobrazhenskaya M.N. ................................... 130, 275
Prezent M.A. ............................................................ 296
Prokhorov N.S. ......................................................... 297
Prolubnikov P.I........................................................... 91
Proskurin G.V............................................................. 62
Prosvirin I.P...................................................... 318, 319
Purygin P.P. .............................................................. 128
Pyatakov D.A. .......................................................... 102
Pyatova E.N. ............................................................. 278
Pyrjaev P.A. ..................................................... 318, 321
N
Nagaoka M. ................................................................ 84
Naghiyeva E.A. ........................................................ 311
Nakatsuji H. ............................................................... 82
Nasirova S.I.............................................................. 311
Nasybullin R.F. ................................................ 218, 245
Naumov V.S. ............................................................ 219
Nazarov P.A. ............................................................ 220
Nebykov D.N. .......................................................... 221
Nechaev M.S. ............................................................. 62
Nedolya N.A. ................................................... 160, 161
Nefedov O.M. .......................................... 197, 226, 289
Nekrasov N.V. ......................................................... 112
Nemukhin A.V. .......................................................... 77
Nenajdenko V.G. ............................................... 43, 261
Neverova O.D. ......................................................... 222
Neyman K.M. ............................................................. 51
Nifantiev N.E. .... 96, 169, 172, 180, 270, 271, 280, 286
Nigmatov A.G. ......................................................... 190
Nikiforova G.G. ....................................................... 248
Nikishin G.I...................................... 189, 191, 237, 298
Nikolaeva E.V. ......................................................... 223
Nikolin V.P. ............................................................. 172
Nikoshvili L.Zh. ....................................................... 107
Nikulshin P.A. .................................. 176, 177, 178, 179
Nindakova L.O. ................................................ 120, 224
Nizhnik Y.P.............................................................. 225
Noel T. ....................................................................... 64
Novikov F.N. ........................................... 133, 227, 299
Novikov M.A. .......................................... 197, 226, 289
Novikov R.A. ................................... 100, 103, 191, 237
Novotortsev V.M. .................................................... 181
Nuriev V..................................................................... 98
Nuzhdin A.L. ........................................................... 321
Nysenko Z.N. ........................................................... 248
O
O’hora P.S. ................................................................. 48
Obruchnikova Ya.A. ................................................ 152
Okhapkin A.I............................................................ 228
Omelchuk O.A. ........................................................ 275
Orekhova M.V. ........................................................ 180
Orlov N.V. ....................................................... 229, 263
Orlova G.I. ............................................................... 280
Oro L.A. ..................................................................... 42
Osipov A.O. ............................................................. 262
Osipov S.N. ................................................................ 32
Ostapenko G.I. ................................................. 128, 129
Ovchinnikova O.G. .................................................. 297
Q
Qi C.-R. ............................................................ 239, 240
R
Radulov P.S. ............................................................. 298
Radychev N.A. ......................................................... 184
332
Rakitin O.A. ............................................................. 241
Raksha E.V. ............................................................. 242
Ratmanova N.K. ............................................... 140, 243
Razinov A.L. ............................................................ 171
Razuvaev A.G. ......................................................... 219
Reshetnikov S.I. ....................................................... 321
Rodina L.L. .............................................................. 225
Rodinovskaya L.A. .......................................... 305, 324
Rodygin K.S. ............................................................ 244
Rogachev A.V. ......................................................... 101
Rogov V.A. .............................................................. 320
Romanov V.V. ......................................................... 225
Romanovska I.I. ....................................................... 233
Romashov L.V. .......................................................... 90
Rozhdestvenskaya N.N. ........................................... 176
Rozhin I.I. ................................................................ 164
Rubaylo A.I. ............................................................. 312
Rubin M. ...................................................... 65, 73, 115
Rubina M. .................................................................. 73
Rubio-Perez L. ........................................................... 42
Ryabchuk P. ............................................................... 73
Ryzhakov A.V.......................................................... 225
Ryzhikov S.B. .......................................................... 150
Ryzhkov F.V. ........................................................... 245
Ryzhov A.N. .................................................... 246, 247
Sevastyanov O.V. ..................................................... 233
Shaikhutdinova R.Z. ................................................. 175
Shakirova Z.R........................................................... 105
Shamanaev I.V. ........................................................ 320
Shamov A.G. ............................................................ 223
Shandryuk G.A. ........................................................ 155
Sharipov M.Y. .......................................................... 257
Shashkov A.S. .................. 172, 175, 235, 255, 280, 297
Shchekotikhin A.E. .......................................... 130, 275
Shcherbinin D.V. ...................................................... 210
Shelimov B.N. .......................................................... 189
Shergold I.A. ............................................................ 258
Shesterenko E.A. ...................................................... 233
Shestopalov A.M. ............................................. 305, 324
Shevelev S.A. ........................................... 122, 135, 222
Shi J. ......................................................................... 259
Shibata N. ................................................................... 38
Shinkarev E.D. ......................................................... 260
Shirinian V.Z. ................................................... 199, 200
Shkineva T.K. ........................................................... 135
Shmatova O.I. ........................................................... 261
Shneider M.M........................................................... 255
Shorunov S.V. .......................................................... 262
Shteingarts V.D. ....................................................... 236
Shtil A.A. ................................................................. 227
Shubina E.S. ............................................................... 87
Shults E.E. ................................................................ 172
Shyshkanov S.A. ...................................................... 263
Silantyev G.A. ............................................................ 87
Sim Y.-K. ................................................................. 264
Sinopalnikova Y.S. ................................................... 265
Sinyashin O.G. ........................................................... 33
Siska P. ..................................................................... 274
Sitdikov V.D............................................................. 287
Sitnikov N.S. ............................................................ 250
Skobelev I.Y. ............................................................ 322
Slyusar O.I. ............................................................... 152
Smirnov A.N. ........................................................... 115
Smirnov B.B. ............................................................ 269
Smirnov K.S. ............................................................ 194
Smirnova L.A. .......................................................... 219
Smol’yakov A.F. ...................................................... 282
Smolenskii E.A......................................... 213, 246, 247
Sokolov M.N. ........................................................... 101
Sokolova O.O. .......................................................... 218
Solovyovа S.A. ......................................................... 283
Somai Magar K.B. .................................................... 121
Spasyuk D. ............................................................... 156
Stakheev A.Yu. .... 53, 80, 215, 216, 217, 266, 267, 268
Starikova Z.A. .......................................................... 165
Starodubtseva E.V. ................................................... 281
Starosotnikov A.M. .................................................. 122
Stashina G.A............................................................. 304
Statsyuk V.E. ............................................................ 129
Stein B.D. ................................................................. 107
Stepanenko R.N. ....................................................... 172
Stepien M. .................................................................. 41
Stopinski J. ......................................................... 94, 208
Stroganov O.V. ......................................... 133, 227, 299
Stroylov V.S. .................................................... 133, 299
Stroylov V.V. ........................................................... 227
Struchkova M.I. ................................................ 182, 300
Studer A. .................................................................... 13
S
Sadokhina N.A. ........................................................ 215
Sadykov E.Kh. ......................................................... 224
Saeys M. ........................................................... 313, 314
Sagirova Zh.R. ......................................................... 281
Sagnou M. ................................................................ 227
Said-Galiev E.E. ....................................................... 248
Saigakova N.A. ........................................................ 126
Saito M. ...................................................................... 45
Sakaki S. .................................................................... 40
Sakharov A.M. ......................................................... 248
Salikov R.F. ............................................................. 124
Salnikov V.A. ........................................................... 178
Samet A.V. ....................................................... 249, 254
Sanzheeva E.R. ................................................ 160, 161
Schafer H. .................................................................. 85
Schegravina E.S. ...................................................... 250
Schluter D. ................................................................. 85
Schmalz H.-G. .......................................................... 250
Schmidt F.K. ............................................................ 276
Sedenkova K.N. ............................................... 119, 251
Sedykh A.E. ............................................................. 252
Segawa H. .................................................................. 83
Seidova Kh. H. ......................................................... 315
Seitkalieva M.M. ...................................................... 253
Selvam P. ................................................................. 217
Semakin A.N. ............................................................. 66
Semenov M.E. .......................................................... 164
Semenov S.L. ........................................................... 132
Semenov V.V. .................................................. 249, 254
Semenova M.N. ....................................................... 254
Senchenkova S.N. ............................................ 235, 255
Sergeeva A.V. ............................................................ 80
Serushkina O.V. ....................................................... 222
Serykh A.I. ............................................................... 256
333
Suffert J. ..................................................................... 44
Suisse I. .................................................................... 113
Sukhanova A.A. ....................................................... 269
Sukhonosova E.V. .................................................... 128
Sukhorukov A.Yu. ..................................................... 66
Sukhova E.V. ................................................... 270, 271
Sulman E.M. ............................................................ 107
Sun Ch.-M. ............................................................... 272
Sun Y.-D. ................................................................. 239
Sunoj R.B. .................................................................. 47
Surov A.O. ............................................................... 273
Suvorova I.A. ........................................................... 151
Svirshchevskaya E.V. .............................................. 250
Svirskaya N.M. ........................................................ 312
Svitanko I.V. ............................................ 133, 227, 299
Szolcsanyi P. ............................................................ 274
U
Uchuskin M.G. ......................................................... 201
Umstead W.J. ............................................................. 28
Ushakov I.A. ............................................................ 224
Ustynyuk Yu.A......................................................... 152
Ustyuzhanina N.E. .................................................... 286
V
Vahitova Yu.V. ........................................................ 193
Valova T.M. ............................................................. 185
Van Der Eycken E.V. ................................................. 79
Van Der Eycken J. ...................................................... 64
Vardapetyan A.A. ..................................................... 171
Vargaftik M.N. ........................................................... 80
Vasilenko D.A. ......................................................... 119
Vasiliev M.A. ........................................................... 129
Vasilyev A.V. ............................................................. 68
Vatsadze I.A. ............................................................ 135
Vatsadze S. ................................................................. 98
Vener M.V. ............................................................... 291
Vereshchagin A.N. ................................................... 284
Vereshchagina N.V. ................................................. 283
Veselov I.S. ................................................................ 81
Vil` V.A............................................................ 285, 294
Vill V.A. ................................................................... 214
Villemson E.V. ......................................................... 163
Vinnitsky D.Z. .......................................................... 286
Vinogradov M.G. ..................................................... 281
Vlasenko R. Ya. ....................................................... 172
Vlasova L.I. .............................................................. 287
Voit A.V. .................................................................. 288
Voitovich Yu.V. ....................................................... 250
Volchkov N.V. ......................................... 197, 226, 289
Volkova M.O. ........................................................... 290
Volozhantsev N.V. ................................................... 255
Vorobyeva D.V. ......................................................... 32
Voronin A.P. ............................................................ 206
Voronin A.V. ............................................................ 291
T
Tang X.-D. ............................................................... 293
Taran O.P. ................................................................ 318
Tarasova A.V. .......................................................... 100
Tarasova O.A. .................................................. 160, 161
Tartakovsky V.A. ............................................... 66, 269
Teleguina N.S. ................................................. 216, 266
Terada M. ................................................................... 55
Terent`ev A.O. ......................................... 189, 285, 294
Terent’ev A.O. ................................................. 232, 257
Terentev A.O. ..................................... 46, 191, 237, 298
Terentiev A.O. ......................................................... 214
Thoang H.S. ............................................................. 112
Tikhomirov A.S. .............................................. 130, 275
Titov I. Yu. ............................................................... 299
Titov I.J. ................................................................... 227
Titov I.Yu................................................................. 133
Titova Yu.Yu. .......................................................... 276
Tkachenko O.P. ................................................ 136, 277
Tolstikov G.A. ......................................................... 172
Tolstikova T.G. ........................................................ 172
Tomilov Y.V. ........................................................... 100
Tomilov Yu. V. ........................................................ 287
Tomilov Yu.V. ......................................................... 124
Trapeznikova O.A. ................................................... 143
Traven V.F. .............................................................. 162
Trenin A.S. ............................................................... 280
Tri N......................................................................... 112
Trivelli X.................................................................... 97
Trofimov B.A. .................................................. 160, 161
Trushkov I.V. ............................................... 72, 81, 163
Tsebrikova G.S. ....................................................... 278
Tsirulnikova N.V. .................................................... 279
Tsishchuk I.E. ............................................................ 32
Tsivadze A.Yu. ........................................................ 278
Tsvetkov D.E. .......................................................... 280
Tsvetkov Y.E. .................................. 169, 172, 270, 271
Tsyganov D.V. ......................................................... 254
Tuktarov A.R. .......................................................... 105
Tulyabaev A.R. ........................................................ 105
Turova O.V. ....................................... 80, 267, 268, 281
Turovskij N.A. ......................................................... 242
Tyurin A.P................................................................ 282
W
Wang B.J. ................................................................... 70
Waser J. ...................................................................... 35
Werner I. .................................................................... 61
Wijaya N. ................................................................. 314
Wong K.-M. ............................................................. 158
Wu R.B. ...................................................................... 70
Wu W.-Q. ................................................. 166, 292, 293
X
Xie F. ........................................................................ 302
Y
Yagafarov N.Z. ........................................................... 74
Yakhvarov D.G. ......................................................... 33
Yamada K. .................................................................. 86
334
Yamashita K. .............................................................. 83
Yang S.-R. .................................................................. 92
Yanina A.M.............................................................. 199
Yanybin V.M. .......................................................... 105
Yaremenko I.A. ........................................ 232, 285, 294
Yarovenko V.N. ....................... 132, 185, 186, 187, 295
Yashtulov N.A. ........................................................ 194
Yashynsky D.V. ............................................... 270, 271
Yogeswara Rao D. ..................................................... 71
Yu C.H. .................................................................... 316
Yu G.-A.................................................................... 158
Yu Y. ........................................................................ 301
Yudin A.K. ................................................................. 26
Yurpalova T.A. ........................................................ 233
Yuvchenko A.P. ....................................................... 123
Zaporotskova I.V. ..................................................... 317
Zarezin D.P............................................................... 261
Zavarzin I.V. ............ 132, 144, 187, 295, 296, 304, 324
Zayakin E.S. ............................................................. 295
Zdorovenko E.L. ...................................................... 297
Zdvizhkov A.T. ................................................ 191, 298
Zefirov N.S. ...................................................... 119, 251
Zeifman A.A............................................. 133, 227, 299
Zemtsov A.A. ............................................. 50, 196, 300
Zhang M. .......................................................... 301, 302
Zhang Q. ................................................................... 259
Zhao Y. ....................................................................... 70
Zharkov M.N. ........................................................... 303
Zharov A.A. ............................................................. 304
Zhdankina G.M. ....................................................... 269
Zheng H. ................................................................... 259
Zheng M.-F. ............................................................. 292
Zhou Zh. ................................................................... 259
Zhu N. ...................................................................... 158
Zlotin S.G. .......................... 56, 190, 198, 269, 281, 303
Zubarev A.A. .................................................... 305, 324
Zubritskij M.Yu ........................................................ 242
Z
Zaikovsky V.I. ......................................................... 216
Zalesskiy S.S. ................................................... 165, 252
Zalewska K. ............................................................. 127
Zalomaeva O.V. ....................................................... 322
335