Centre in Green Chemistry and Catalysis - CCVC

Transcription

Centre en chimie verte et catalyse
La chimie réinventée pour un avenir plus propre
Chemistry reinvented for a cleaner tomorrow
Centre in Green Chemistry and Catalysis
P-01
Orthonickelated Phosphinite Complexes Derived from Substituted
Phenols and Naphthols
Loïc Mangin, Boris Vabre, and Davit Zargarian
Université de Montréal, 2900 Edouard-Montpetit Blvd, Montreal, QC H3T 1J4
E-mail of presenting and corresponding author: [email protected] ,
[email protected]
Cyclometalated complexes are key intermediates in catalytic C-H functionalization reactions.[1]
Even though nickel precursors have been involved in various C-H functionalization reactions
such as alkylation and trifluoromethylation of aromatic amides[2], to date only a few
cyclonickelated species have been isolated and characterized.
We have recently reported on the synthesis and full characterization of cyclonickelated
complexes derived from Csp2-H activation of aryl-phosphinites.[3] These species react with
electrophiles such as PhCH2Br or CH3C(O)Cl to yield ortho-functionalized phenols. This poster
will report on new cyclonickelated complexes derived from substituted phenols or naphthols.
The discussion will focus on the regioselectivity of the nickelation step.
[1] (a) Bedford, R. B.; Betham, M.; Charmant, J. P. H.; Haddow, M. F.; Orpen, A. G.; Pilarski, L. T.; Coles, S.
J.; Hursthouse, M. B. Organometallics 2007, 26, 6346. (b) Bedford, R. B.; Hazelwood, S. L.; Horton, P. N.;
Hursthouse, M. B. Dalton Trans. 2003, 4164.
[2] (a) Aihara, Y.; Chatani, N. J. Am. Chem. Soc. 2013, 135, 5308. (b) Song, W.; Lackner, S.; Ackermann, L.
Angew. Chem. Int. Ed. 2014, 53, 2477.
[3] Vabre, B.; Deschamps, F.; Zargarian, D. Organometallics 20
P-02
Efficient Microwave-assisted Synthesis of Magnetically Recoverable AgFe3O4@CMC Nanoparticle Catalysts for Carbonyl Compounds
Hydrogenation
Alain Li, Madhu Kaushik, Chao-Jun Li, and Audrey Moores
Department of Chemistry, McGill University, 801 Sherbrooke St. West,
Montreal, Quebec, H3A 2K6, Canada
Iron oxide nanoparticles can be used as magnetic supports that enable an easy catalyst
recovery at the end of a chemical reaction. By grafting metal nanoparticles catalysts on them,
they can contribute to more sustainable and greener industrial processes. The synthesis of AgFe3O4@CMC for aldehyde hydrogenation catalysis was investigated. Under very short
microwave irradiation conditions, silver and iron nanoparticles were grafted on an inexpensive
polymer support, carboxymethyl cellulose (CMC).
Analyses show that the particles obtained were small and monodispersed (<20 nm) in the
organic matrix. The obtained magnetic nanoparticles were tested for the catalytic
hydrogenation of aldehydes in water, showing similar performances to their homogeneous
counterpart without the use of expensive ligands or additives.
1
R. B. Nasir Baig, R. S. Varma, Green Chem. 2013, 15, 398-417.
1
1
P-03
S. Horikoshi, H. Abe, K. Torigoe, M. Abe, N. Serpone, Nanoscale 2010, 2, 1441-1447.
Z. Jia, F. Zhou, M. Liu, X. Li, A. S. C. Chan, C.-J. Li, Angew. Chem. Int. Ed. 2013, 52, 11871-11874.
TOWARDS THE SYNTHESIS OF MONOFLUOROALKENE-BASED DIPEPTIDE
ISOSTERES
Myriam Drouin, Audrey Gilbert and Jean-François Paquin*
Canada Research Chair in Medicinal and Organic Chemistry, PROTEO, CGCC, Chemistry
Department, Université Laval, Québec, QC, Canada, G1V 0A6
Solid-state 19F NMR is a useful tool to study biological events such as protein interactions with
biological membranes.1 Given the fact that monofluoroalkenes are non-hydrolyzable peptide
bond mimics,2 we wish to explore their potential use as backbone molecular probes.
Starting from 3,3-difluoropropenes, our research group has reported new ways to obtain
monofluoroalkenes via transition metal catalysis3 or by using Li-based reagents.4 Our progress
towards the synthesis of monofluoroalkene-based dipeptide isosteres will be discussed.
(1) Ulrich, A. S. Prog. Nucl. Magn. Reson. Spectrosc. 2005, 46, 1.
(2) Choudhary, A.; Raines, R.T. ChemBioChem 2011, 12, 1801.
(3) (a) Pigeon, X.; Bergeron, M.; Barabé, F.; Dubé, P.; Frost, H.N.; Paquin, J-F. Angew. Chem. Int.
Ed. 2010, 49, 1123. (b) Hamel, J.-D.; Drouin, M.; Paquin, J.-F. J. Fluorine Chem. 2015, in press.
(4) (a) Bergeron, M.; Johnson, T,; Paquin, J.-F. Angew. Chem. Int. Ed. 2011, 50, 11112. (b)
Bergeron, M.; Guyader, D.; Paquin, J.-F. Org. Lett. 2012, 14, 5888.
P-04
Friedel-Crafts Reaction of Benzylic Fluorides Through a Selective
Activation of C-F Bonds by Hydrogen-Bonding
Pier Alexandre Champagne, Yasmine Benhassine, Justine Desroches and
Jean-François Paquin
Département de chimie, 1045, avenue de la Médecine, Université Laval, Québec
(Québec), Canada, G1V 0A6.
Nucleophilic substitution of alkyl fluorides generally requires harsh conditions to proceed.1 In
acidic conditions, C-F bonds react efficiently with various Brønsted and Lewis acids, as well as
with carbocations and silylium ions. C-F bond substitution is also possible with very basic and
nucleophilic reagents, usually benefitting from stabilizing metal-fluorine interactions (often
lithium). Under neutral conditions however, C-F activation could only be effected by transitionmetal catalysis.
We have recently described that various hydrogen-bond donors (HBD) are potent activating
agents for C-F bond substitution in mild and neutral conditions. Herein, we will describe the
selective Friedel-Crafts reactivity of benzylic fluorides in the presence of HFIP, a stronger HBD.
This reaction provides access to 1,1-diarylmethanes in good yields starting from a wide array of
benzylic fluorides and electron-neutral to electron-rich arenes.2 We will present the
optimization of the reaction conditions, scope of benzylic fluorides and arenes, along with a
mechanistic proposal fully supported by comprehensive experimental evidence.
1
Amii, H.; Uneyama, K. Chem. Rev. 2009, 109, 2119.
Champagne, P. A.; Benhassine, Y.; Desroches, J.; Paquin, J.-F. Angew. Chem. Int. Ed. 2014, 53,
13835
2
P-05
Regioselective Palladium-Catalyzed Tsuji-Trost Reaction of
Trifluoromethyl and Pentafluorosulfanyl Derivatives
Justine Desroches, Rémy Hemelaere and Jean-François Paquin*
Département de chimie, 1045 avenue de la Médecine, Université Laval,
Québec, QC, Canada G1V 0A6
Email: [email protected]
A 4,4,4-trifluorobut-2-ene chain attached to a phenolic oxygen has been shown over the years
to be a useful fluorinated substituent in medicinal chemistry, agrochemistry and material
sciences.1 The main synthetic strategy used to produce such compounds, a SN2 reaction, has
limitations.1 Therefore, we became interested in developing an alternative strategy. Herein, we
report the first use of a regioselective Tsuji-Trost reaction catalyzed by palladium nanoparticles
for the introduction of a 4,4,4-trifluorobut-2-ene chain starting from 1 and using a wide variety
of nucleophiles (phenols, amines, malonates).2 As the SF5 group is considered as a "super-CF3",
we have also developed a similar reaction starting from the pentafluorosulfanyl analog 2.
1
(a) Krastel, P.; Schmitt, E.; Meingassner, J. G.; Liechty, B.-M.; Schreiner, E. P. Patent WO2009/24527
A1, 2009. (b) Miyashita, Y.; Kutose, K.; Tomida, K.; Yamada, S. Eur. Patent EP1911350 A1, 2008. (c)
Kelly, S. M.; Skelton, G.; Jones, C.; Minter, V.; Tuffin, R. Mol. Cryst. Liq Cryst. Sci. Technol., Sect. A
2001, 364, 873−880.
2
Hemelaere, R.; Desroches, J.; Paquin, J.-F. Org. Lett. 2015 (DOI: 0.1021/acs.orglett.5b00539).
P-06
Synthesis of nitriles through dehydratation of aldoximes and amides
using XtalFluor-E
Mathilde Vandamme, Massaba Keïta and Jean-François Paquin*
Canada Research Chair in Organic and Medicinal Chemistry, CCVC,
Département de chimie, Université Laval, Québec, QC, G1V 0A6
[email protected]
Nitriles are versatile building blocks for the preparation of various compounds, including
pharmaceuticals, agrochemicals and materials. The dehydratation of aldoximes and amides is
one of the common methods for their preparation. However, most of the reagents used are
either highly reactive or expensive, and only a few conditions allow the synthesis of chiral
nitriles. Herein, we described the formation of nitriles from both aldoximes and amides using
XtalFluor-E ([Et2NSF2]BF4).1 The optimization of the reaction conditions and the scope of this
new transformation will be presented.2 Excellent isolated yields were obtained (up to 99%)
under mild conditions. This method allowed the synthesis of a wide range of cyanides including
aromatic, vinylic, benzylic, and aliphatic (including chiral ones).
1.
2.
(a) Beaulieu, F.; Beauregard, L.-P.; Courchesne, G.; Couturier, M.; Laflamme, F.;
L’Heureux, A. Org. Lett. 2009, 11, 5050–5053. (b) L’Heureux, A.; Beaulieu, F.; Bennet, C.;
Bill, D. R.; Clayton, S.; Laflamme, F.; Mirmehrabi, M.; Tadayon, S.; Tovell, D.; Couturier, M.
J. Org. Chem. 2010, 75, 3401–3411.
Keïta, M.; Vandamme, M.; Paquin, J.-F. In preparation.
P-07
The SN2’ Reaction of 3-Fluoro-3-Halopropenes: A Versatile Entry Towards
Monofluoroalkenes
Jean-Denys Hamel, Myriam Drouin and Jean-François Paquin
Université Laval, Department of Chemistry, Quebec, Quebec, G1V 0A6
Owing to their strong structural and electronic similarity with amide bonds, monofluoroalkenes
(2a-b) are used as non-hydrolyzable isosteres in drug discovery. However, their synthesis still
represents a challenge in certain cases.1
In this context, based on previous work by Gouverneur2 and our group3, the Pt-catalyzed allylic
amination of 3,3-difluoropropenes (1) was first explored. The reaction uses easily-accessed
Pt(PPh3)4 as a catalyst, proceeds under mild conditions and showcases an interesting case of C-F
bond activation. However, thorough evaluation of the scope of the reaction revealed severe
limitations in terms of substrates and nucleophiles tolerated.4
To counter these limitations, we proposed the use 3-chloro-3-fluoropropenes (3) as
monofluoroalkene precursors. Early results showed that no catalyst is now required for allylic
substitution to occur, allowing for a remarkably broader range of nucleophiles to be used. Thus,
selected results towards the use of C-, N-, O-, P- and S-nucleophiles will be presented.
(1) Landelle, G.; Bergeron, M.; Turcotte-Savard, M.-O.; Paquin, J.-F. Chem. Soc. Rev. 2011, 40,
2867. (2) Benedetto, E.; Keita, M.; Tredwell, M.; Hollingworth, C.; Brown, J. M.; Gouverneur, V.
Organometallics 2012, 31, 1408. (3) Pigeon, X.; Bergeron, M.; Barabé, F.; Dubé, P.; Frost, H. N.;
Paquin, J.-F. Angew. Chem. Int. Ed. 2010, 49, 1123. (4) Hamel, J.-D.; Drouin, M.; Paquin, J.-F. J.
Fluorine Chem. 2015, in press. DOI: 10.1016/j.jfluchem.2014.07.012
P-08
Decarboxylative and Desulfinative Palladium-Catalyzed Cross-Coupling
Reactions using Continuous-Flow Chemistry
Cindy Buonomano, Mickael Holtz-Mulholland and Pat Forgione*,
Department of Chemistry & Biochemistry, Concordia University, Montréal,
QC, H4B 1R6 and Centre in Green Chemistry and Catalysis,
[email protected]
Heteroaromatics (3) are key motifs present in many biologically interesting compounds. Their
synthesis can be achieved via palladium-catalyzed cross-coupling reactions. Classical methods
suffer from the use of stoichiometric amounts of organometallic reagents and longer reaction times.
Recently, decarboxylative and desulfinative cross-couplings have streamlined as advantageous
alternative to classical methods. To further increase the attractiveness of these cross-couplings for
industrial applications, it is essential to adjust them to new synthetic technologies, such as
continuous-flow processes. Flow chemistry is a powerful technique that shows some benefits such
as control of heat transfer and mixing, concentration and stoichiometry versus the batch processes
commonly used in organic synthesis. This process can provide easy automation, and improved
safety and reproducibility. The main objective of this research project is to use the carbone-carbone
bond formation methodology developed by our group, and make it more efficient and versatile
using the flow chemistry techniques (Equation 1). The final goal of this project would lead to the
one-flow multi-step synthesis of isoquinoline-derived compounds (6) and improvement of the
synthetic pathway reducing the formation of side-products (Equation 2). This project will allow us
to synthesize heteroaromatics compounds in a greener and more effective way.
P-09
Synthesis of isocyanides through dehydration of formamides using
XtalFluor-Epyrazoles
Massabe Keïta, Mathilde Vandamme, Olivier Mahé and Jean-François
Paquin*
Canada Research Chair in Medicinal and Organic Chemistry, PROTEO, CGCC,
Chemistry Department, Université Laval, Québec, QC, Canada, G1V 0A6
Isocyanides (also called isonitriles) are key building blocks in organic synthesis. They are well
known for their use in Ugi reaction (or other multicomponent reactions), but they are also utilized
in many other synthetic transformations and a few natural products contain this functionality. A
straightforward approach for their preparation consists in the dehydration of formamide.
Numerous reagents can affect this transformation. Unfortunately, some of these reagents are
expensive and not available on large scale, in addition most are either hygroscopic, moisture
sensitive, highly toxic or thermally unstable. We have recently described the synthesis of various
N-containing heterocycles1 through dehydration using diethylaminodifluorosulfinium
tetrafluoroborate ([Et2NSF2]BF4), XtalFluor-E,2 a crystalline solid initially developed as a
deoxofluorinating agent with enhanced thermal stability. As a potential extension of this work, we
imagined that if formamides were used as starting substrate, upon activation with XtalFluor-E and
in the presence of a base, isocyanides would be generated. Herein, we reported the feasibility of
this transformation.3 A wide range of formamides can be used to produce the corresponding
isocyanides in up to 99% yield. In a number of cases, the crude products showed good purity
(generally >80% by NMR) allowing to be used directly in multi-components reactions.
1.
(a) Pouliot, M.-F.; Angers, L.; Hamel, J.-D.; Paquin, J.-F. Org. Biomol. Chem. 2012, 10, 988–
993. (b) Pouliot, M.-F.; Angers, L.; Hamel, J.-D.; Paquin, J.-F. Tetrahedron Lett. 2012, 53, 4121–
4123
2.
(a) Beaulieu, F.; Beauregard, L.-P.; Courchesne, G.; Couturier, M.; Laflamme, F.; L’Heureux,
A. Org. Lett. 2009, 11, 5050–5053. (b) L’Heureux, A.; Beaulieu, F.; Bennet, C.; Bill, D. R.; Clayton, S.;
Laflamme, F.; Mirmehrabi, M.; Tadayon, S.; Tovell, D.; Couturier, M. J. Org. Chem. 2010, 75, 3401–
3411.
3.
Keïta, M.; Vandamme, M.; Mahé, O.; Paquin, J.-F. Tetrahedron Lett. 2015, 56, 461–464.
P-10
Copper-Catalyzed Hydroamination of Alkynes with Aliphatic Amines:
Regioselective Access to (1E,3E)-1,4-disubstituted-1,3-dienes
J. Bahri,1,3 F. Monnier,1 B. Jamoussi,2 M. Taillefer 1*
1
Institut Charles Gerhardt Montpellier, [email protected],
[email protected] 5253, AM2N, 8 Rue de l'École Normale,
34296 Montpellier Cedex 05, France. 2 ISEFC / Materials LaboratoryMolecules and Applications, Technical Sciences, Tunisia. 3 Département de
chimie, Pavillon Alexandre-Vachon, Université Laval, 1045 avenue de la
Médecine,
Québec
(Québec)
G1V
0A6,
Canada.
E-mail:
[email protected]
Hydroamination of alkynes is a desirable transformation leading to C–N bond formation.
It offers a direct route to the synthesis of nitrogen-containing organic molecules such as
enamines or imines, which can readily undergo further transformations to generate
valuable nitrogen-containing compounds. The high atom economy makes hydroamination
highly attractive, because no intrinsic by-products are formed. In our laboratory, we
developed the hydroamination of terminal aryl alkynes such as phenylacetylene and
several of its derivatives with cyclic secondary amines by using copper catalysis (CuCl).
This method allows the regioselective formation of (1E,3E)-1,4-disubstituted-1,3-dienes
with good yields (40-76%). The geometry of this product was confirmed by X-ray
crystallography. The electronic nature of the arylacetylene substituents (R) plays a major
role in the generalization of the reaction.1
1
J. Bahri, B. Jamoussi, A. Lee, M. Taillefer, F. Monnier, Org. Lett., 2015, 17, 1224-1227.
P-11
On the Frontier between Nucleophilic Aromatic Substitution and Catalysis
Martin Pichette Drapeau,a,b Thierry Ollevier,a and Marc Tailleferb
a Département de chimie, Pavillon Alexandre-Vachon, Université Laval, 1045
avenue de la Médecine, Québec (Québec) G1V 0A6, Canada. E-mail:
[email protected]
b Institut Charles Gerhardt Montpellier, UMR 5253, AM2N, ENSCM, 8 rue de
l’École Normale, 34296 Montpellier Cedex 05, France, E-mail:
[email protected]
A study on the arylation of heteroatom nucleophiles using haloarenes without added
metal catalysts is presented. Backed by an unexpected enhancement effect in the
-diketone additives for iodoarenes substituted by both electronwithdrawing and donating groups, a discussion on the involvement of traces of metals is
suggested, even though efforts were made to eliminate them as much as possible. We
believe that the frontier between nucleophilic aromatic substitution and metal catalysis
will likely prove to be much harder to delimit than is generally thought.1
Without metal (EWG only)
OH
R
X
+
SN Ar ?
R'
Catalysis ?
O
R
R'
R' = EWG, EDG
With b-diketones: positive effect
EWG: reduced reaction times
EDG: reactions efficient even without metal catalysts
1
Pichette Drapeau, M.; Ollevier, T.; Taillefer, M. Chem. Eur. J. 2014, 20, 5231.
P-12
Asymmetric Hydrosilylation of Ketones Using Chiral Iron Complexes
Hoda Keipour and Thierry Ollevier*
Département de chimie, Pavillon Alexandre-Vachon, Université Laval, 1045
avenue de la Médecine, Québec (Québec) G1V 0A6.
[email protected]
Reduction of unsaturated compounds containing C=C, C=N and C=O bonds is among the
most studied and probably the most diversified reactions. This work focuses on the study
of the asymmetric iron-catalyzed reduction of C=O double bonds. In this project, we have
developed methods for the asymmetric hydrosilylation of ketones catalyzed by chiral iron
and other metals complexes, using hydrosilanes as reductants.
In order to find the optimal reaction conditions, we used diamine and C 2-symmetrical
ligands with various iron and other metals sources. Promising results have been obtained
in terms of yields and enantioselectivities for ligands bearing a diamine moiety in the
presence of Zn(OAc)2, ZnEt2 and Co(OAc)2 as a catalyst and (EtO)2MeSiH as a reducing
agent.
P-13
Synthesis of Phenols through Transition-Metal-Free Arylation of Water
Pierre-Louis Lagueux-Tremblay, Di Meng, Martin Pichette Drapeau
and Thierry Ollevier*
Département de chimie, Pavillon Alexandre-Vachon, 1045 avenue de la
Médecine, Université Laval, Québec (Qc), G1V 0A6
The synthesis of phenols has a great importance in the chemical industry. However, the
industrial syntheses, using high temperatures and pressures, are difficult to carry out in
academia. Methods based on copper and palladium, associated with the appropriate
ligands, were recently described for the synthesis of phenols under milder conditions. In a
green chemistry perspective, we developed a transition-metal-free method which avoids
the use of toxic and expensive transition metals and ligands. This new method only requires
water as a precursor of hydroxide anions, an inexpensive base, potassium tert-butoxide,
and DMSO. Based on the ratios of phenol isomers, we suggest an aryne type mechanism.
P-14
Synthesis of metal-organic structures from low-valent metals by redoxpromoted mechanochemical self-assembly
Martin Glavinović, Feng Qi, Athanassios D. Katsenis, Tomislav Friščić* and
Jean-Philip Lumb*
Department of Chemistry, McGill University
Metal-organic complexes and coordination polymers have emerged as promising modern
materials for a variety of applications.[1] While there have been brilliant innovations in their
architectural and functional designs, the underlying synthetic methodologies have undergone
little fundamental change.[2] Today, metal-organic complexes are synthesized through a
combination of acid-base and ligand exchange transformations in solution involving metal salts.
This synthetic pathway, which is highly dependent on the use of organic solvents, elevated
temperatures or pressures, requires the use of strong bases, or the production of corrosive
mineral acids as by-products.
This poster will describe a novel methodology for the solvent- and waste-free synthesis of
paramagnetic materials, directly from low-valent metals and metal oxides.[3] The synthetic
strategy couples the oxidative potential of o-quinones with coordination-driven self-assembly
involving nitrogen-based ligands. This provides a one-pot, multi-component mechanochemical
oxidative assembly,[4] which affords well-defined, paramagnetic metal-organic complexes
possessing semiquinonate ligands. The utility of the method is highlighted by the waste-free
synthesis of a porous paramagnetic material, setting the stage for the evaluation of these
materials in a range of applications.
[1]: Chem. Rev. 2012, 112, 673-674
[2]: Stock, N.; Biswas, S.; Chem. Rev. 2012, 112, 933-969
[3]: Green Chem., 2013, 15, 2121-2131
[4]: Chem. Sci., 2012, 3, 2495-2500
P-15
Iridium-Catalyzed Direct Dehydroxyation of Alcohols,
Jian-Lin Huang, Xi-Jie Dai, and Chao-Jun Li*
(Department of Chemistry, McGill University)
Alcohols, derived from biomass, constitute a highly attractive class of chemical feedstocks
because they are abundant and easily accessible. Direct dehydroxylation of alcohols to the
corresponding hydrocarbons is a fundamentally important reductive process that encompasses
a vast array of applications ranging from biomass refinery industry to pharmaceutical synthesis.
Up to date, although numerous synthetic methodologies have been developed to fulfill the
conversion from alcohols to hydrocarbons, few of them can be recognized as efficient
processes from the synthetic perspective.
The main challenge in the development of one-step dehydroxylation reaction is the poor
strong base hydroxide anion to be generated. To overcome these intrinsic problems, most
known tactics, have been designed toward obtaining more reactive intermediates with better
leaving groups from alcohols.
We have successfully developed an iridium-catalyzed direct dehydroxylation protocol for
alcohols, via an oxidation/ Wolff-Kishner reduction sequence, which highlights a useful
alternative to the classical multistep dehydroxylation of alcohols.
P-16
Recyclable, Supported and Homogeneous Noyori-Ikariya Catalyst for
Asymmetric Transfer Hydrogenation in Water
Dauphinais, M.; Zimbron, J. M.; Charette, A. B.
(Département de chimie, Université de Montréal)
We would like to present the elaboration of a new kind of support for the Noyori-Ikariya
hydrogen transfer catalyst. The new, recyclable complex features both increased activity
and enantioselectivity compared to other such nitrogen-linked supported catalysts. In
addition, the novel support is installed with ease on a ligand, and is inert towards
practically all common functional groups. The reactions are run in water as solvent, with
the only reagents being environmentally benign formic acid and triethylamine. The small
molecular weight of the support as well as the simplicity of its incorporation to the metal
center allow for atom economy, and the only by-product of the reaction besides the
leftover reagents is carbon dioxide. Ultimately, the sub-percent loading of the catalyst
and the possibility to recycle it several times without loss of activity provide for a very
low requirement in rare metal.
P-17
A New Class of Tunable Heterocyclic Fluorophores: Divergent Synthesis
through Catalytic C-H Arylations
Lévesque, É.; Constantineau, L.; Bechara, W. S.;
Pelletier, G.; Charette, A. B.
Visible light-emitting fluorescent organic compounds are extensively used tools in microscopy
for the precise tracking of specific molecules in biological systems. Unfortunately, most of the
commonly employed fluorescent cores suffer from a narrow variability of the absorption and
emission wavelengths, and the effects of substituents on these wavelengths are often difficult
to predict.
This presentation reports the discovery of a previously unknown tetracyclic structure with
interesting photochemical properties. These benzo[a]imidazo[2,1,5-cd]indolizines are readily
functionalized in a divergent synthetic pathway to yield a library of fluorescent probes with
emission wavelengths covering the entire visible spectrum. This highly efficient synthesis
involves up to two catalytic direct C-H arylations and has an overall yield up to 65% (for 5 or 6
linear steps) from commercially available materials. DFT calculations are able to rationalize and
predict photochemical properties, allowing the precise tuning of these properties by selecting
the functional groups attached to the core. Various reactive functional groups can be linked to
the core without affecting photochemical properties, enabling the tethering of the fluorophore
to biomolecules. This new class of fluorescent probes is remarkable for their high chemical
stability, their insensitivity to pH variations and their unusually high Stokes shift (up to 230nm).
P-18
Development of an enantio- and diastereoselective Simmons-Smith
bromocyclopropanation reaction and mechanistic considerations
Taillemaud, S.; Charette, A. B.
Ranked among the 10 most used cycles for the ellaboration of small drug molecules,1 the
cyclopropane subunit is a key backbone for the pharmaceutical industry. Thus, new strategies
to access and allow efficient functionalisation of such moieties are needed. Recently, our group
published various Simmons-Smith type methodologies to access chloro-2, fluoro-3 and
iodocyclopropanes4 in good yields and presenting excellent selectivities, starting from allylic
alcohols. However, no method has ever been described allowing to access bromocyclopropanes
in such manner, yet being key intermediates toward more functionnalized architectures. 5, 6,7 ,8
With this work, we are glad to report the first enantioselective bromocyclopropanation
reaction thanks to extensive NMR analyses, allowing us to deduce the mechanism of the
carbenoid formation in standard conditions and its true nature. Unprecedently high yields were
therefore obtained by making adjustments to reduce wastes and make the reaction more
efficient.
1
Taylor, R. D.; MacCoss, M.; Lawson, A. D. G. J. Med. Chem. 2014, 57, 5845.
Beaulieu, L.-P. B.; Zimmer, L. E.; Gagnon, A.; Charette, A. B. Chem. Eur. J. 2012, 18,
14784.
3
Beaulieu, L.-P. B.; Schneider, J. F.; Charette, A. B. J. Am. Chem. Soc. 2013, 135, 7819.
4
Beaulieu, L.-P. B.; Zimmer, L. E.; Charette, A. B. Chem. Eur. J. 2009, 15, 11829.
5
Overman, L. E.; Ricca, D. J.; Tran, V. D. J. Am. Chem. Soc. 1997, 119, 12031.
6
Shi, J.; Manolikakes, G.; Yeh, C.-H.; Guerrero, C. A.; Shenvi, R. A.; Shigehisa, H.;
Baran, P. S. J. Am. Chem. Soc. 2011, 133, 8014.
7
Tucker, J. W.; Stephenson, C. R. J. Org. Lett. 2011, 13, 5468.
8
Banning, J. E.; Gentillon, J.; Ryabchuk, P. G.; Prosser, A. R.; Rogers, A.; Edwards, A.;
Holtzen, A.; Babkov, I. A.; Rubina, M.; Rubin, M. J. Org. Chem. 2013, 78, 7601.
2
P-19
Palladium-Catalyzed Direct Functionalization of Alpha-Cyclopropyl Amino
Acid-Derivatives
Ladd, C. L.; Charette, A. B.
In the last ten years, extensive progress has been made in the area of direct C–H
functionalization and the synthetic utility of these reactions has been demonstrated.
Cyclopropanes represent an underexplored target for direct functionalization, despite their
known reputation as widely used motifs in current top-selling market pharmaceutical and
agrochemicals. Within this class of compounds, cyclopropyl amino acids are unique substrates
that have found interesting applications in peptidomimetics as the cyclopropyl moiety can
impart greater rigidity leading to enhanced biological activity. However, accessing cyclopropyl
amino acids and their derivatives remains a challenging synthetic problem. The development of
a palladium-catalyzed direct functionalization approach towards accessing cyclopropyl alphaamino acid derivatives will be described.
P-20
Rapid access to 3-aminoindazoles from aromatic tertiary amides
Régnier. S.; Cyr, P.; Bechara, W. S.; Charette, A. B.
A two-step synthesis of structurally diverse 3-aminoindazoles from readily available
starting materials was developed. This sequence includes a one-pot synthesis of
aminohydrazones through chemoselective triflic anhydride mediated activation of
aromatic tertiary amides, followed by subsequent addition of tosyl protected hydrazide.
These precursors then participate in an intramolecular ligand-free palladium catalyzed C–
H amination reaction. The azaheterocycles thus obtained were further diversified through
subsequent deprotection/functionalization reactions.
P-21
Synthesis of , -Unsaturated α-Aminoketones Using a Tandem CopperCatalyzed Vinylation Reaction Followed by a Claisen Rearrangement
Simon Ricard, Alexandre Gagnon et Benoit Daoust
(Department of Chemistry, UQAM et UQTR)
Our laboratory recently developed an efficient method for the preparation of non natural
amino acids from amides using two consecutive copper-catalyzed coupling reactions (CCC)
followed by a Claisen rearrangement.1 In the present study, we report our progress on the
synthesis of ,-unsaturated -aminoketones starting from carbamates. Our strategy
involves the CCC between carbamate (1) and vinyl diiodide (2) (easily prepared from
readily available alkynes). This first step has been achieved with excellent yields (>95%)
and very short reaction times (30-120 minutes). The β-iodo-vinylated carbamate thus
obtained is then coupled with allylic alcohol (3) to produce, after heating, the desired
compound (4) through a Claisen rearrangement. These scaffolds can be transformed into
various α-amino carbonylated compounds via a few functional group transformations.
Details of the synthetic method and experimental procedures will be presented.
R2
1)
O
R1O
(1)
N
H
PG
2) R4
3) 
I
(2) R
3
(3)
I

"Cu"
OH "Cu"
O
R1O
R4
N 
PG
(4)

R2
R3
O
S. Ricard, N. Rahem, G. Sanapo and B. Daoust, “Synthesis of ,-Unsaturated Aminoaldehydes Using Two Consecutive Copper-Catalyzed Vinylation Reactions Followed
by a Claisen Rearrangement”, Manuscript in preparation.
1
P-22
Synthesis and Reactivities of New NCN-Type Pincer Complexes of Nickel
Jean-Philippe Cloutier, Boris Vabre, Berline Moungang-Soumé and Davit
Zargarian*
Département de chimie, Université de Montréal, Montréal (Québec),
Canada H3C 3J7
[email protected]
The poster will describe the preparation, characterization and reactivities of a new family of
Ni(II) complexes based on the tridentate NCN-type pincer ligands 1,3-bis(pyrazole),5-R-C6H3
(R= H, OMe). Refluxing these ligands in xylene with a nickel(II) precursor and NEt3 gave the
complexes (NCNpz)NiBr and (MeO-NCNpz)NiBr via C-H nickelation. Reaction of the bromo
complexes with aq. H2O2 gave the functionalized ligands Br-NC(OH)Npz and NC(OH)Npz or
MeO-NC(OH)Npz, whereas 1 reacted with I2 to generate (NCNpz)NiBr·I2, an iodine adduct
displaying weak Br—I interactions. Heating 1 in EtOH in air generated NC(OEt)Npz, and this
ligand derivatization could be extended to other alcohols and amines. The possible mechanism
involving a Ni(III) species of this reaction will be described.
P-23
Design and application of versatile, fluorescent DNA nanothermometers
David Gareau and Alexis Vallée-Bélisle
Developing nanomaterials, probes, switches or nanomachines that are able to respond to
specific temperature changes should prove of utility for several applications in the fields of in
vivo imaging, clinical diagnostics, and drug-delivery. Here, we describe various bio-inspired
strategies to engineer DNA thermoswitches with programmable linear response ranges for
precise temperature sensing between 25°C to 95°C. Using structural modifications or
inexpensive DNA stabilizers, we show that we can tune the transition mid-points of DNA
thermometers from 30°C to 85°C. Using multimeric switch architectures, we are able to create
ultrasensitive thermometers that display large 20-fold, quantitative signal changes within only
7°C. Lastly, by combining thermoswitches of different stabilities, or a mix of stabilizers of
various strengths, we can create extended thermometers that respond linearly up to 50°C in
temperature range. Using these programmable DNA thermometers we measured, for the first
time, the temperature equilibration time inside PCR wells using a fluorescent readout. Their
potential applications in in vivo imaging, DNA nanomachines, drug delivery systems and
synthetic biology are further discussed.
P-24
Supramolecular photo-catalytic systems: Ru photosensitizers and Co
photocatalysts
a
Olivier Schott , Daniel Chartranda, Amlan K. Pala, Garry S. Hanan,a
a
Université de Montréal, Département de Chimie, 2900 EdouardMontpetit, Montréal,QC, H3T 1J4
Contact information : [email protected]
Nature has used sunlight as its main energy source to oxidize water and fix CO2 to
produce carbohydrates for over a billion years. In the context of development of sustainable
energy, the field of artificial photosynthesis attempts to mimic nature by extracting electrons
from water and reducing protons or others organic compounds (e.g., CO2) in order to store solar
energy in chemical bonds.1 The following work is focused on the reduction of protons.2 In this
work, polypyridine based Ru photosensitizers are investigated in association with oxime-based
Co catalysts in different conditions (various wavelengths of irradiation, various concentrations,
organic or aqueous media).3 Structure-catalytic activity relationships are also discussed. The
couple Ru(diphenyl-[2,2'-bipyridine]-4,4'-dicarboxamide)(bipy)2][PF6] and Co(chg)2ClPyridine
(chg=cyclohexane1-2dione oxime) proves to have promising activity.
(1)
Frischmann, P. D.; Mahata, K.; Wuerthner, F. Chem. Soc. Rev. 2013, 42, 1847.
(2)
Artero, V.; Chavarot-Kerlidou, M.; Fontecave, M. Angew Chem Int Ed Engl 2011,
50, 7238.
(3)
Rousset, E.; Chartrand, D.; Ciofini, I.; Marvaud, V.; Hanan, G. S. Chem Commun
2015, in press.
P-25
One Pot Synthesis and Reactivity of a New Class of Mesoionic Imidazolium
Heterocycles
Huseyin Erguven, B. Arndtsen*
Dept. of Chemistry, McGill University, 801 Sherbrooke St. W. Montreal, QC
H3A 0B8
The cycloaddition of 1,3-dipoles with dipolarophiles can provide an efficient and
convergent method to generate heterocycles. In this work, a new type of 1,3-dipole and its
reactivity towards dipolarophiles is investigated. We have found that mesoionic
imidazolium heterocycles can prepared in one step by reacting an imine with pyridyl acid
chlorides in the presence of base. These products can undergo 1,3-dipolar cycloaddition
with alkynes, thereby opening a new and modular synthetic approach to generate
indolizines. The diversity of 1,3-dipoles available via this method, their properties and
structures, as well as their 1,3-dipolar cycloaddition reactivity, will be discussed.
P-26
Synthesis and characterization of discrete Re(I) assemblies via a [nx1]
directional bonding strategy
Baptiste Laramée-Milette,1 Christophe Lachance-Brais,1 and Garry S.
Hanan*,1
1
Université de Montréal, Montréal, QC H3T 2B1, [email protected] (presenting author)
Over the past few decades, self-assembly of simple components has led to the synthesis of
remarkable materials such as molecular cages, macrocycles, helices, grids, and MOFs.1 Although
there are several ways to build complex assemblies, the directional bonding approach is quite
straightforward and probably the most useful for the construction of rigid assemblies.2 However, it
usually requires two separate entities, an organic donor ligand and a metallic acceptor, reacting
together in perfect symbiosis in order to arrive at the final assembly.
In our ongoing project, the discrete self-assembly of two Re(I) squares was achieved by a simple
and efficient [4x1] strategy where the complexes, [Re(4-pytpy-κ2N)(CO)3Br] and [Re(4-pytpyκ3N)(CO)2Br], act as their own ligands. The photophysical and electrochemical properties of the
assemblies and their precursors will be presented along with solid-state X-ray diffraction studies.3
1
D. L. Caulder and K. N. Raymond, Acc. Chem. Res. 1999, 32, 975
R. Chakrabarty, P. S. Mukherjee and P. J. Stang, Chem. Rev. 2011, 111, 6810.
3
B. Laramée-Milette, C. Lachance-Brais and G. S. Hanan, Dalton Trans. 2015, 44, 41.
2
P-27
Self-assembled benzimidazolium salts as strong antibacterial and non-toxic
materials
Elie Claude-Rosny et Andreea Schmitzer
The development of low molecular weight synthetic anion transporters remains an important
subject in medical research and yet, the need of these compounds increased with the discovery of
the numerous genetic diseases involving chloride channels. Indeed, this growing interest comes
from the considerable number of diseases originating in dysfunctions of natural anion channels
such as in the case of cystic fibrosis, but also from the well known relationship between microbial
cell death and their membrane disruption. The membrane perturbation usually results in an
electrolyte imbalance process, involving nitrate and chloride anions. In consequence, the
development of new paradigms to induce anion imbalance in living cells particularly in
antibiotherapy may constitute an interesting alternative treatment circumventing multidrugresistance.
Herein, we describe an economical and ecological syntheis of different benzimidazolium salts
displaying potent antimicrobial activity and low toxicity against human cells. The mechanism of
action of these benzimidazolium salts on bacterial membranes was assessed by bioanalytical
techniques including assays in model membrane liposomes, membrane depolarization studies and
scanning electron microscopy (SEM) in living bacteria.
P-28
Diazepane carboxylate catalyzed Diels-Alder reactions of α-branched α,βunsaturated aldehydes
Nicklas Häggman and James L. Gleason
The Diels-Alder reaction is one of the most utilized reactions in organic chemistry and the iminium
catalyzed Diels-Alder reaction of α,β-unsubstituted aldehydes, has been well studied. However,
these catalysts typically are not compatible with α-branched aldehydes, most likely due to
increased steric hindrance preventing iminium formation.
We have developed a 1,2-diazepane-carboxylate catalyst which together with an acid co-catalyst
efficiently catalyzes the cycloaddition of sterically encumbered aldehydes. Use of this catalytic
method provides high yields, great exo-selectivity and a wide substrate scope, exemplified by its
ability to perform novel Diels-Alder reactions, such as α-methylcinnamaldehyde with
cyclopentadiene. Chiral versions of the catalyst are currently under investigation and show
promising preliminary results.
P-29
Environmentally Friendly Desulfinative Cross-Coupling of Heteroaromatic
Sulfinates with Aryl Triflates
Daniel Mangel and Pat Forgione
(Department of Chemistry & Biochemistry, Concordia University)
[email protected]
Aryl-substituted heteroaromatics are a key motif in a variety of applications including medicinal
chemistry, natural products, advanced materials, and the agrochemical industry. As a consequence
of this versatility, these structures have attracted much attention of the scientific community in
developing novel, efficient, methods for accessing these scaffolds. Aryl-substituted
heteroaromatics were synthesized via desulfinative cross-coupling reactions using aryl triflate and
heteroaromatic sulfinate coupling partners. This method uses synthetically versatile aryl triflates to
access aryl-substituted heteroaromatics in good yields employing aqueous and alcoholic media
without the use of base, additives or co-catalysts.
P-30
A TEMPO-free Copper-Catalyzed Aerobic Oxidation of Alcohols
Boran Xu, Elizabeth Hartigan, Jean-Philip Lumb* and Bruce A. Arndtsen*
Dept. of Chemistry, McGill University, 801 Sherbrooke St. W. Montreal, QC
H3A 0B8
The oxidation of alcohols to their corresponding aldehydes and ketones is a fundamentally
important reaction in organic synthesis. While many methodologies exist for this transformation,
they all suffer from the drawback of generating stoichiometric amounts of oxidant waste. In
principle aerobic oxidation can emerge as a “greener” platform for this transformation as the use
of molecular oxygen as the terminal oxidant only generates water as the byproduct. Currently
many developed systems suffer from limited substrate scope and/or pressing reaction conditions.
We describe our efforts towards developing a more active Cu-catalyzed aerobic oxidation catalyst,
capable of oxidizing challenging substrates such as primary or secondary aliphatic alcohols, in good
synthetic yields and under mild reaction conditions. Mechanistic details of catalyst activity will be
discussed as well as chemoselectivity compared with regards to current systems.
OH
R1
R2
Cu/DBED/DMAP(cat.)
O2 (1 atm)
4Å M.S. rt
O
R1
R1, R 2 = aryl, heteroaryl, allyl and alkyl
R2
Cu cat:
tBu H
N
CuLn
N
tBu H
PF 6
Tyrosinase Mimic
P-31
Palladium Catalyzed Synthesis of Polycyclic Pyrroles from Aryl Iodides, CO
and Alkyne-Tethered Imines
Neda Firoozi and Bruce A. Arndtsen*
Dept. of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal,
QC, H3A 0B8
The pyrrole nucleus is widespread in natural products and pharmaceuticals, such as the
cholesterol-lowering drug atorvastatin and the antiinflamatory analgesic tolmetin. It has therefore
become important to develop efficient and convenient methods to synthesize these heterocycles.
A number of synthetic methods to prepare pyrroles have been described, including the 1,3-dipolar
cycloaddition of Münchnones with alkynes. In this work, polycyclic pyrroles have been synthesized
by intramolecular palladium catalyzed reaction of alkyne-tethered imines, CO and aryl iodides. This
transformation is proposed to proceed via the in situ, carbonylative generation of Münchnones,
which undergo rapid alkyne cycloaddition. The design of catalysts for this reaction, its mechanism,
and the diversity of pyrrole products available, will each be discussed.
[1] S. Simsek, C.G. Schalkwijk, B.H.R. Wolffenbuttel, Diabetic Med. 2012, 29, 628.
P-32
Palladium Catalyzed Synthesis of Münchnones: A Multicomponent Route to
Pyrroles
G. Martin Torres and Bruce A. Arndtsen*
Department of Chemistry, McGill University, 801Sherbrooke Street West,
Montreal, QC, Canada H3A 0B8
Pyrroles have found use in a broad variety of areas, ranging from components in biologically
relevant compounds, to materials science and polymers. Nevertheless, approaches to construct
pyrroles, especially highly substituted variants typically require multistep synthesis. These can be
time consuming, create significant waste with each step, and make the generation and tuning of
pyrroles an involved, iterative process. In recent years, multicomponent synthesis has arisen as an
attractive route to prepare complex products from simple building blocks. In this work, a palladium
catalyzed multicomponent synthesis of pyrroles is presented. The building blocks in this reaction
are all simple: imines, aryl iodides, alkynes and CO, and are coupled together in a one pot,
palladium catalyzed cascade. The mechanism of this transformation, catalyst design, reaction
intermediates, and the diversity of pyrrole products available, will each be discussed.
P-33
Stereoselective Amination of Thioethers: Mechanistic studies
Henri Piras, Hélène Lebel*
Université de Montréal
Montréal, Québec, Canada
Email : [email protected]
Our group has recently introduced a chiral N-mesyloxycarbamate as a metal nitrene
precursor, to perform asymmetric C-H amination of alkanes in the presence of Rh(II)
dimers catalysts (Org. Lett. 2011, 13, 5460; Chem. Commun. 2012, 48, 7799). We
present herein the development, the scope and the limitations of the diastereoselective
intermolecular amination of thioethers using a chiral dirhodium(II) carboxylate catalyst to
produce chiral sulfilimines. Despites the importance of these nitrogen analogs of
sulfoxides in medicinal chemistry, their chemistry remains largely underdeveloped,
because of the lack of synthetic methods, especially in the stereoselective manifold.
Using our reaction conditions, a variety of chiral aromatic and aliphatic sulfilimines were
produced in high yields and stereoselectivities (Angew. Chem. Int. Ed. 2014, 53, 7300)
Besides the mild and practical reaction conditions, the method is also environmentally
friendly, as the by-products generated from N-mesyloxycarbamates are biodegradable.
The synthesis of chiral sulfoximines was also achieved. Screening of additives revealed
that a catalytic mixture of achiral DMAP and pyridinium derivative, bis(DMAP)CH2Cl2
was crucial for the stereoinduction of the process. Mechanistic studies have been
performed to elucidate the role of these additives on the reactivity and selectivity of the
amination reaction (J. Org. Chem. 2015, 80, 3572). Results suggested a Rh(II)-Rh(III)
complex as the catalytically active species. Furthermore, diastereoselectivities were
influenced by the sulfonyloxy leaving group, suggesting a rhodium nitrenoid complex.
This is the first time that such a species has been proposed as the active intermediate in
amination reactions. The details of this investigation will be presented.
P-34
C-H propargylic amination using Rhodium dimers.
Johan Bartholoméüs, Hélène Lebel*
Our group has recently developed a method for the formation of C-N bonds by
direct functionalization of C-H bonds using metal nitrene species.
N-Mesyloxycarbamates were used with a rhodium dimer to react with C-H bonds
and thioethers to produce respectively chiral benzylic amines and chiral sulfilimines
(Chem. Commun., 2012, 7799; J. Org. Chem. 2015, 80, 3572). This method was
extended to the synthesis of propargylic amines. The latter are versatile synthetic
blocks for the formation of diverse heterocycles and are also found in many
biologically important compounds. They are typically synthesized by the addition of
an acetylide to an imine, or by reduction of ketamine (Bolm, et al. Chem. Commun.
2006, 4263). In comparison, the direct functionalization of propargylic C-H bonds is
an attractive alternative method which does not use prefunctionalized substrates. In
this poster, the stereoselective amination of propargylic substrates using a chiral
Nmesyloxycarbamate and chiral rhodium dimer catalysts will be presented. A
variety of chiral enantioenriched propargylic amines were produced in good yields
and high levels of stereoselectivity. The optimization of the reaction conditions and
the scope of the reaction will be discussed. Some mechanistic aspects of the
reaction will also be presented.
P-35
Rhodium catalyzed intramolecular C-H amination:
Synthesis of oxazolidinones
Maroua Khalifa, Hélène Lebel*
Oxazolidinones are important biologically active heterocycles which can be found in
a variety of synthetic pharmaceuticals (Curr. Org. Synt. 2007, 81). Our research
group has developed an efficient methodology for intramolecular C-H amination
using an organometallic rhodium (II) dimer as a catalyst and Nmesyloxycarbamates as nitrene precursors (J. Am. Chem. Soc., 2005, 14198). This
direct intramolecular process provides a convenient access to oxazolidinones
without the need of prefunctionalization. Hereby, we want to impart a study of new
reaction conditions and scope with N-mesyloxycarbamate derivatives from primary
and secondary alcohols. New mechanistic hypotheses will also be discussed.
P-36
Advances in Thermal and Photochemical Cu(I)-Catalyzed Macrocyclic
Sonogashira-Type Cross-Couplings.
Jeffrey Santandrea, Anne-Catherine Bédard, Clémentine Minozzi and Shawn
K. Collins*
Département de Chimie, Centre in Green Chemistry and Catalysis, Université
de Montréal, Montréal, Québec, Canada, H3T 1J4,
[email protected]
Macrocyclic products are usually synthesized from a handful of known macrocyclization methods.
Surprisingly, the Sonogashira coupling has yet to be a commonly used method to accomplish
macrocyclizations, despite relatively mild reaction conditions. However, recent examples highlight
the lack of practicality and effectiveness of the reaction on a large scale since significant amounts
of palladium and stoichiometric amounts of copper in a dilute media are needed to afford
benzolactones in poor yields. The development of thermal and photochemical copper-catalyzed
Sonogashira protocols performed at high-concentrations are described as alternatives to Pdcatalyzed methods to access a wider range of compounds and pharmaceutically relevant motifs
such as polyketide-derived resorcyclic acid lactones. (Org. Lett. 2014, 16, 3892-3895.)
P-37
Hydrodynamic Effects of Swelling FPSO on Gas-Liquid Packed Bed Flows
Amir Motamed-Dashliborun, Faïçal Larachi*
(Département de génie chimique, Université Laval, Québec, QC, Canada G1V
0A6)
E-mail address: [email protected]
Floating production storage and offloading (FPSO) as a cutting-edge technology is being employed
for oil/gas field exploitation in deep seas or areas far off continental shores. This type of vessel
combines extraction, production, and storage units on the same floating system which in turn can
reduce the minimum economic field size.1 Apart from the economic standpoint, since FPSOs
comprise waste heat recover systems and gas and seawater treating units, which are considered as
a unique and green technology on sea.
However, swelling sea imposes rocking effects on operating units on board FPSO. To diminish those
detrimental effects, packed beds have been considered as a very appropriate candidate where
reactors and scrubbers are used for hydrocarbon treatments.2 Nevertheless ship motions may
influence fluid flow distribution inside even packed beds which have dramatic impacts on the
performance of units and, thus, being away to meet capacity and product specifications.
To illustrate the effect of ship oscillations on the packed bed hydrodynamics, recently in our group,
a laboratory-scale packed bed with descending gas-liquid cocurrent flows was installed on a
hexapod ship motion simulator and subjected to translational and rotational motions.3 Capacitance
wire mesh sensor was used to experimentally study the two-phase flow dynamic features in
response to different movements. This poster will present some results of this study revealing
significant effects of ship oscillations on the embarked packed bed hydrodynamics.
1. Shimamura, Y., 2002. FPSO/FSO: State of the art. Journal of marine science and technology 7, 5970.
2. Weiland, R.H., Hatcher, N.A., Seagraves, J., 2013. Choosing Tower Internals for LNG, Shale Gas,
and Tail Gas Treating, SOGAT 2013, Abu Dhabi, UAE.
3. Assima, G.P., Motamed-Dashliborun, A., Faïçal Larachi., 2015. Emulation of gas-liquid flow in
packed beds for offshore floating applications using a swell simulation. AIChE Journal, DOI:
10.1002/aic.14816.
P-38
Application of magnetic field assisted mixing with ferrofluids in micromixing
studies of parallel-competitive reactions with mixing dependent product
distribution
Shahab Boroun and Faical Larachi
Chemical Engineering Department, Université Laval, Québec, QC, Canada,
G1V 0A6
Characteristics of transport phenomena in chemical processing have a profound impact on process
economy and efficiency. Designing heat and mass exchangers and also chemical reactors with
efficient technologies of enhanced transport processes reduces power consumption, equipment
size and also increases product quality. In this regard, enhanced homogenization of temperature
and concentration fields is undoubtedly crucial in many practices and more specifically in chemical
synthesis where it affects product distribution in complex reaction systems (1). Furthermore,
development of high performance micromixers in microreaction technology is of essential
importance since transport phenomena in microstructures is diffusion limited. Previous studies
show that ferrofluids can be manipulated when exposed to various types of magnetic fields and
are of potential interest in mixing applications (2). In the current work, we are going to reveal how
a magnetic assisted mixing method can be advantageous in chemical synthesis applications
especially when selectivity of products matters. For this purpose, potassium borate solution,
containing dispersed magnetic nanoparticles (MNPs), and diluted sulfuric acid as the reactants of
instantaneous proton transfer reaction were fed separately into a microfluidic T-mixer. Formation
of iodine as the second competitive reaction is accomplished in the mixer via iodate and iodide
ions present in potassium borate solution. MNPs were synthesized by a coprecipitation method
and were stabilized by trisodium citrate. Uniform rotating and static magnetic fields were
generated by Helmholtz coils and mixing experiments were carried out in presence of magnetic
field while the Reynolds number of reactant streams in the capillary tube is adjusted close to 1.
The larger reaction time constant of iodine formation in comparison to that of proton transfer
reaction enables an indirect evaluation of the mixing rate by measuring total produced iodine
concentration by UV spectrophotometry. Effects of other process variables such as MNPs
concentration and magnetic field frequency on mixing rate are also studied.
(1) Brian P. Mason et al., Chem. Rev., 2007, 107, pp 2300–2318.
(2) P. Hajiani and F. Larachi, Chem. Eng. Process. Process Intensif., 2014, 84, pp 31–37.
P-39
Development of Diazepane Carboxylate Organocatalysts for Asymmetric
Cope Rearrangement and Other Applications
Dainis Kaldre*, James L. Gleason
Department of Chemistry, McGill University, Montreal, Quebec, H3A 0G4,
[email protected]
[3,3]-Sigmatropic rearrangements, particularly the Claisen and Cope rearrangements, have been
extensively applied in organic synthesis. These reactions can generate two new stereocenters in a
single reaction that typically passes through a highly ordered transition state. Since their discovery,
several transition metal and Lewis acid catalyzed variants have been developed. However, only
one organocatalytic [3;3] sigmatropic rearrangement, a hydrogen bond catalyzed Claisen
rearrangement, has been developed up to date. We have developed the first organocatalytic Cope
rearrangement using diazepane carboxylate catalyst 1. The reaction shows remarkable rate
acceleration for a range of substrates. Subsequent studies have shown that organocatalysts of
general structure 2 can be used in an enantioselective Cope rearrangement. Theoretical
investigation of reaction mechanism using DFT revealed a stepwise process involving formation of
a carbocation intermediate that has opened new avenues for iminium catalyzed reactions. Our
studies have also revealed that catalysts 1 and 2 are generally efficient in forming iminium ions
with α-substituted aldehydes. Several applications of these catalysts in other reactions will also be
discussed.
P-40
Adapting a Catalytic Aerobic C-H Functionalization of Phenols to the
Synthesis of Oxindole Heterocycles
Zheng Huang*, Mohammad S. Askari, Xavier Ottenwaelder and Jean-Philip
Lumb
Department of Chemistry and FRQNT Centre for Green Chemistry and
Catalysis, McGill University
ABSTRACT: Phenols are attractive starting materials for organic synthesis due to their availability
from both petrochemical and renewable sources, and their ubiquity in natural products and
biologically active molecules. Nevertheless, direct methods for their functionalization often suffer
from poor selectivity or poor atom-economy. This presentation will describe recent efforts from
our group to develop a catalytic aerobic method for their direct functionalization, and will highlight
its utility in the synthesis of oxindole heterocycles. Mechanistic investigations have revealed the
involvement of a Cu(II)-semi-quinone radical complex as a key, catalytically competent
intermediate. We will discuss the role of this intermediate, particular in its ability to mediate
efficient dehydrogenative coupling. These studies shed new light on the fundamental reactivity of
ortho-quinones, and introduce Cu-semi-quinone radicals as strategic elements of control. The
application of these principles lead to a conceptually novel approach for aromatic C-H
functionalization, whose scope and utility will be discussed.
P-41
Degradation of aqueous glyphosate over graphene –supported sunlightdriven photocatalyst
M. Feriani, K. Belkacemi and S. Hamoudi
Département de Sols et Génie Agroalimentaire, Centre en Chimie Verte et
Catalyse, Université Laval
Photocatalytic oxidation under sunlight is being developed as a green powerful technique for the
treatment of water and wastewaters containing toxic organics such as pesticides. Nowadays,
glyphosate is one of the most abundant pesticides detected in surface and groundwater
worldwide. Glyphosate is highly soluble in water and is classified as toxic to aquatic life with long
lasting effects.(1)
The present work is devoted to the study of the solar-driven photocatalytic degradation reaction
for glyphosate aqueous solutions over graphene-supported N-doped TiO2 photocatalyst. The
specific objectives are: (i) Catalyst synthesis and characterization; and (ii) Optimization of process
conditions to achieve total pesticide degradation.
The catalyst was characterized using nitrogen adsorption, powder X-ray diffraction, TEM, UV-Vis,
FTIR, and XPS. The reaction tests were operated at room temperature and atmospheric pressure.
Aliquots of the solution were collected at appropriate time intervals and analyzed using HPLC.
The synthesized catalyst was found to be very effective in totally degrading glyphosate under
visible light within 45 min of reaction while P25 TiO2 was totally inactive under comparable
reaction conditions.
1) GHS/CLP-Regulation (EC) No 1272 (2008), Annex VI, Table 3–1, List of harmonized
classification and labeling of hazardous substances, pp. 235.

To whom correspondence should be addressed. E-mail: [email protected]
P-42
Removal of Cr (VI) from Aqueous Solutions Using Amino-Functionalized
Carbon Nanospheres
N. Benadji-Hamidi1,2,3, Z. Bendjama2, K. Bachari3, S. Hamoudi1
1
Département des Sols et de Génie Agroalimentaire, Centre en chimie verte
et catalyse, Université Laval.
2
Laboratoire de Génie des Procédés Industriels, Université des Sciences et de
la Technologie Houari Boumediene (U.S.T.H.B.), Alger (Algérie).
3
Centre de Recherche Scientifique et Technique en Analyses PhysicoChimiques, Alger (Algérie).
Heavy metals discharged to the environment from several industries represent a serious threat to the
fauna and flora of lakes and streams. Moreover, heavy metal ions are highly toxic and can be
accumulated in the human body and lead to cancer, even at low concentration. Hexavalent
chromium (Cr(VI)) was listed as one of the 25 most hazardous substances (1). Adsorption
represents one of the potential methods for the removal of heavy metals ions from water.
In this study graphitized carbon nanospheres (CNs) were synthesized and used as adsorbent for the
removal of Cr(VI) from water. CNs were further functionalized with surface amino groups and their
adsorptive performances were compared with those obtained with the bare CNs. Both materials
were characterized using nitrogen adsorption, XRD, TEM and FTIR techniques. The adsorption
tests were performed batchwise and showed that the amino-functionalized CNs outperformed the
bare CNs under several operating conditions.
1) ATSDR. Agency for Toxic Substances and Disease Registry, Detailed data for 2011 priority list
of hazardous substances. Available from: http://www.atsdr.cdc.gov/SPL/ index.html .
P-43
Combining Click-Unclick Diels-Alder Chemistry with oxa-Michael
Addition/Elimination: A New, Powerful Reaction Cascade for Constructing
Furo[2,3-b]chromones
Muddala Ramesh, Charles Thibault and John Boukouvalas*
Department of Chemistry, Laval University, Quebec City, Quebec G1V 0A6,
Canada; e-mail: [email protected]
P-44
Towards chemoselective arylation reactions of peptides using
triarylbismuthanes
Martin Hébert, Adrien Le Roch, Alexandre Gagnon*
Université du Québec à Montréal, 2101, rue Jeanne-Mance, Montréal,
Québec, H2X 2J6
E-mail of presenting and corresponding author : [email protected] , [email protected]
There is a need for general methods that lead to post-synthetic modification of peptides.
Currently, few methods exist for the chemoselective arylation on specific amino acid
residues. Organobismuth reagents have
recently gained interest due to their
versatility in bond formation, functional
group tolerance, low cost and low
toxicity related to the inorganic bismuth
salt. Recently, our group has developed
efficient arylation methods using highly
functionalized trivalent arylbismuth
reagents to form C‒C, C‒O and C‒N
bonds.1 In particular, indoles, phenols
and aminoalcohols have been
successfully arylated in good to excellent
yields via substoichiometric copper
catalysis in mild conditions. As a result, this method will be further employed as a mean of
selective arylation of polypeptides. In this poster, we will present our progress in the
development of arylation methods of peptides using triarylbismuthanes.
1
a) Petiot, P.; Gagnon, A. Eur. J. Org. Chem., 2013, 5282; b) Crifar, C.; Petiot, P.; Ahmad, T.;
Gagnon, A. Chem. Eur. J., 2014, 20, 2755; c) Petiot, P.; Dansereau, J.; Gagnon, A. RSC Adv.,
2014, 4, 22255; d) Petiot, P.; Dansereau, J.; Hébert, M.; Khene, I.; Ahmad, T.; Samaali, S.;
Leroy, M.; Pinsonneault, F.; Legault, C. Y.; Gagnon, A. Org. Biomol. Chem., 2015, 13, 1322.
P-45
Copper-Catalyzed O-Arylation of N-Protected 1,2-Aminoalcohols using
Functionalized Organobismuth Reagents
Tabinda Ahmad and Alexandre Gagnon*
Département de Chimie de l'UQAM
2101, rue Jeanne-Mance, Montréal, QC, H2X 2J6, Canada
Corresponding email address: [email protected]
An efficient protocol for the copper-catalyzed O-arylation of N-protected 1,2-aminoalcohols
using functionalized triarylbismuth reagents was developed. Catalytic amount of copper acetate
promoted a C–O cross-coupling reaction under mild conditions. This reaction tolerates a wide
diversity of functional groups giving access to a range of β-aryloxyamines which are important for
the synthesis of medicinally relevant compounds and natural products.
1. Pauline Petiot, Julien Dansereau, Martin Hébert, Imene Khene, Tabinda Ahmad, Samira
Samaali, Maxime Leroy, Francis Pinsonneault, Claude Y. Legault and Alexandre Gagnon,
Org. Biomol. Chem., 2015, 13, 1322-1327.
2. Cynthia Crifar, Pauline Petiot, Tabinda Ahmad and Alexandre Gagnon, Chem. Eur.
J., 2014, 20, 2755-2760.
3. Pauline Petiot, Julien Dansereau and Alexandre Gagnon, RSC Advances, 2014, 2225522259.
P-46
Efficient hollow sunlight-driven energy storage photocatalysts for the
degradation of organic pollutants under visible light and in the dark
C.-C Nguyen, N. N. Vu and T.-O. Do*
Department of Chemical Engineering, Laval University, Quebec, G1V 0A8,
CANADA
Hollow structure has received a great deal of attention in the field of photocatalysis due to
its unique nano-architecture which not only possesses a high surface area, but also can
enhance light absorption. Furthermore, due to the drawback of photocatalysts that can only
function under light irradiation, the development of sunlight-driven energy storage
photocatalysts which can work both in light and dark, e.g., it can store electrons in the light
and further discharge in the dark for pollutant degradation, is particularly interested. Here
we report a new type of hydrogen-treated hollow Pt-WO3/TiO2-Au based nanospheres. This
type of hollow nanocomposites has not only high surface area and strong sunlight
absorption, but also highly efficient electron-hole separation and high electron storage
capacity. As a result, this nanocomposite exhibits a remarkable improvement in
photoactivity for the degradation of formaldehyde both under visible light and in dark as
compare to that of conventional photocatalyst.
P-47
Synthesis of Advanced Tungsten-Based Heterogeneous Catalysts for LiquidPhase Oxidative Cleavage of Oleic Acid
Amir Enferadi Kerenkan and Trong-On Do*
Department of Chemical Engineering, Université Laval, Québec, Canada G1V
0A6
Abstract:
Oils and fats of vegetable and animal origin have recently attracted a growing interest as
renewable materials for feedstock in oleochemical industries. This attention arises from not only
the environmental reasons, but also economic ones. Unsaturated fatty acids can be converted into
mono- and di-carboxylic acids, which are applicably valuable materials, through oxidative cleavage
reaction (OCR) in the presence of a highly efficient catalyst/oxidant system. In this work, three
types of advanced heterogeneous catalysts have been developed; (i) pure tungsten oxide, (ii)
mesoporous alumina supported tungsten oxide and (iii) surfactant capped tungsten oxide. After
characterizing by BET, SEM, XRD and TGA, the synthesized catalysts were employed in the OCR of
oleic acid using H2O2 as oxidant. GC-MS was used to determine the produced amounts of desired
products, azelaic and pelargonic acids. The results showed more than 90% conversion for types (i)
and (iii) catalysts in 5 h reaction with high selectivity for azelaic and pelargonic acids. The catalyst
type (ii) although has higher stability, showed less conversion (78%).
(A)
(B)
Scheme: Oxidative cleavage of oleic acid into aldehydes (A) and over-oxidation into carboxylic
acids (B).
P-48
Cu2O Microcrystals as an Efficient Catalyst in A3-Coupling Reaction
Huizhi Bao, Audrey Moores*
Department of Chemistry, McGill University, 801 Sherbrooke St. West,
Montreal, Quebec,H3A 2K6, Canada
The transition-metal catalyzed three-component coupling of an aldehyde, an alkyne and an
amine, called A3-coupling reaction, has been established as a convenient and general
approach towards propargylamine. Cu-based catalysts has been investigated as an
outstanding candidate in A3-coupling reaction. Herein, well-defined Cu2O microcubes and
octahedra, exposing exclusively (100) and (111) surface plane respectively, are synthesized
successfully and demonstrated as efficient catalysts.
The results present that Cu2O microcrystals are able to achieve almost 100% yield only in 5
minutes at 100 oC; furthermore, they have moderate to high yields when the reaction
temperature is low as 40 oC within several hours (3-5 hrs). Interestingly, the octahedra
exhibit better activity than the cubes, due to the existence of coordinated unsaturated Cu
atom on (111) surface plane. The discovery develops fundamental understanding in
mechanical aspect of A3-coupling reaction.
P-49
Study of the electrophilic potential of diazirines and application to the
synthesis of heterocycles
Yoann Schneider and Claude Y. Legault*
Département de chimie, Université de Sherbrooke, Sherbrooke, QC, J1K 2R1,
[email protected]
Diazirines are well-known molecules, with the ability to be a source of
electrophilic nitrogen. Yet, this potential was never truly exploited until
recently. The diazirine derived from adamantanone circumvents the issues
that prevented its wide use. Addition of nucleophilic reagents lead to the
formation of corresponding N-monosubstituted species or N,N-disubstituted
hydrazones, by addition of an electrophile afterward. They can release their
corresponding hydrazines, which are converted to heterocycles in good
yields. The adamantanone can be recovered in 80-100% yields. This
methodology demonstrates the potential of diazirines as electrophilic
nitrogen sources with a recoverable protecting group.
P-50
Single-Site Studies of Stereocontrol by Chemisorbed Chiral Molecules
Yi Dong1, Guillaume Goubert1, Jean-Christian Lemay1, Michael N. Groves2,
Katrine L. Svane2, Bjørk Hammer2, Peter McBreen1.
1
Department of Chemistry, Laval University, Québec City, Canada, G1V 0A6,
2
Interdisciplinary Nanoscience Center (iNano) and Department of Physics and
Astronomy. Aarhus University,DK 8000 Aarhus, Denmark.
E-mail : [email protected]
Isolated adsorbed chiral molecules can stereodirect prochiral co‐adsorbates on
surfaces and the application of this phenomenon underpins a method to perform
asymmetric heterogeneous catalytic reactions. Typically, the stereochemical action
is attributed to intermolecular interactions in complexes formed by docking the
prochiral substrate in a chiral pocket created by the chemisorbed chiral molecule.
We will present results from a combined variable temperature STM and optB88vdW DFT study of individual bimolecular docking complexes. The complexes were
formed between enantiopure 1-(1-naphthyl)ethylamine and -ketoester and phenyl ketone substrates on Pt(111). The experiments reveal sub-molecularly
resolved and time-resolved site-specific and stereospecific data. The results show
that a single chemisorbed enanantiomer simultaneously presents several chiral
pockets, each displaying a specific prochiral ratio. A hierarchy of metal-molecule
and molecule-molecule interactions is found to control prochiral selection at any
given site. Time-lapsed STM measurements of individual substrate molecules
sampling a set of chiral pockets reveal critical information on the dynamics of
stereocontrol. By comparison to DFT calculated structures, images and energies,
the STM measurements also isolate elementary hydrogenation and
dehydrogenation reaction steps.
P-51
Room Temperature Synthesis of Allenamides by a CopperCatalyzed SN2’ Reaction from Propargylic Bromides
Emeline Benoit, Charles S. Demmer, Gwilherm Evano
Laboratoire de Chimie Organique, Department of ‘‘Chimie et Physico-Chimie Organiques’’,
Université Libre de Bruxelles, Avenue F. D. Roosevelt, 50, CP160/06, B-1050 Brussels,
Belgium
Contact Information: [email protected], [email protected]
Due to their remarkable reactivity, allenamides represent an especially attractive
class of building blocks and their chemistry has been extensively studied recently. The
polarization of the allene due to the presence of the nitrogen atom makes them ideal
candidates for the development of new reactions. They have indeed been shown to be
excellent substrates in a wide range of reactions such as metalations or cycloadditions and
have also been used for the total synthesis of various natural products.1
However, if their chemistry has been considerably developed,1 current methods
available for their synthesis still suffer from major limitations such as the need for stepwise
sequences, poor substrate scope or limited availability of the starting materials required. In
an attempt to address these limitations, several methods based on copper catalysis have
been recently developed for the synthesis of allenamides by cross-coupling between
nitrogen nucleophiles and bromo- or iodo- allenes.2 If these transformations typically afford
allenamides in low-to-fair yields, they rely of the use of halogenated allenes, which are
often tricky to prepare and rather unstable, and thermal activation, which can be
incompatible with certain allenamides.
In this context, we have developed a novel approach for the synthesis of
allenamides based on a copper-catalyzed formal SN2’ reaction relying on the use of readily
available propargylic bromides as starting materials. The development of this reaction,
which proceeds at room temperature in most cases, as well as its scope and limitations will
be presented.
O
Z
R1
1
NH
R2
+
H
Br
R4
5
R
CuTC cat.
2,2'-bipyridine cat.
Cs2CO3
CH3CN, rt
O
Z
R1
H
N
R2
•
R4
R5
For a review on the chemistry of allenamides, see: Lu, T.; Lu, Z.; Ma, Z.-X.; Zhang, Y.;
Hsung, R. P. Chem. Rev. 2013, 113, 4862.
2
(a) Trost, B. M.; Stiles, D. T.; Org. Lett. 2005, 7, 2117. (b) Shen, L.; Hsung, R. P.; Zhang,
Y.; Antoline, J. E.; Zhang, X. Org, Lett. 2005, 7, 3081. (c) Persson, A. K. A.; Johnston, E.
V.; Bäckvall, J.-E. Org. Lett. 2009, 11, 3814.
P-52
Magnetic MnFe2O4-Graphene Composite for Efficient Removal of
Glyphosate from Water
N. Ueda Yamaguchi1,2; R. Bergamasco2 and S. Hamoudi1
1
Département de Sols et Génie Agroalimentaire, Centre en Chimie Verte et
Catalyse, Université Laval
2
Department of Chemical Engineering, Universidade Estadual de Maringá,
Maringá, Paraná, Brazil
Graphene is believed to be one of the most interesting materials of this
century. Features like large surface area and unique two-dimensional
structure make single sheets of graphene attractive adsorbent candidate for
water purification. However, the use of graphenic materials for large-scale
water purification is limited due to the difficulty of their separation.
Therefore, magnetically recoverable composites using for instance MnFe2O4
nanoparticles combined with graphene offer a judicious alternative making
possible such application.
The present poster will focus mainly on (1) the synthesis and characterization
of hybrid graphene-magnetic MnFe2O4 nanoparticles via a simple one-step
solvothermal method and (2) the application of the synthesized material as a
new adsorbent for efficient removal of glyphosate, a toxic herbicide, from
water.
P-53
Groupe de recherche en chimie radioanalytique et environnementale
Marie-Ève Lecavalier, Dominic Larivière
Département de chimie, Université Laval
La radioécologie étudie le devenir des radionucléides dans les écosystèmes,
selon les objectifs de protection de l’environnement, des humains et du
biote. Les mesures de radioactivité dans les échantillons d’air, d’eau, de sols
et d’organisme vivants sont à la base de toute étude radioécologique.
Cependant, plusieurs des approches présentes pour la mesure de la
radioactivité génèrent une empreinte environnementale importante. À l’aide
des principes de la chimie verte, nous développons des outils analytiques plus
efficaces, générant moins de déchets (incluant ceux radioactifs) et
permettant un suivi en continu et en temps réel de ces polluants.
P-54
Nanocomposite of graphitic carbon nitride and titanate for photocatalytic
hydrogen production under visible light
Mohammad Reza Gholipoura, Francois Bélandb Trong-On Doa*
a
Department of Chemical Engineering, Laval University, Québec, G1V 0A8,
b
SiliCycle Inc. 2500, Boul. du Parc-Technologique, Québec, G1P 4S6
Hydrogen production via photocatalytic water splitting using sunlight has an
enormous potential to solve the worldwide energy and environmental crisis.
Nanocomposite heterojunctions of various semiconductors can extend light
absorption capacity as well as increase charge carrier lifetimes by improving
charge separation. This kind of nanocomposite photocatalyst improves
quantum efficiency by providing a large surface area and nanoparticle size.
Graphitic carbon nitride (g-C3N4) is one of the best semiconductors for
hydrogen evolution because of its conduction band edge, narrow band gap
and high chemical stability. In this work, we combine nanosheets of graphitic
carbon nitride with titanate nanodisk in order to increase charge separation
and improve quantum efficiency. After synthesizing nanodisk of titanate,
these nanodisks are deposited on the separated nanosheets of g-C3N4. Then
different metals act as cocatalysts are deposited on the surface of titanate. As
a result, in the presence of sacrificial reagents, hydrogen evolution increases
noticeably under visible light irradiation.
P-55
Design of a photocatalytic material for mineralization of volatile organic
compounds
a
Mathieu St-Jean , Stéphane Chabotb , Serge Kaliaguinea and Trong-On
Doa*
a
Department of Chemical Engineering, Laval University, Québec, G1V 0A8
b
Exp Inc., 5400 Boul. des Galeries, Québec, G2K 2B4
Exp Inc. is an engineering company who developed and commercialized an
advanced oxidation process for degradation of volatile organic compounds.
Their process is based on a homogeneous catalyst which generates OH
radicals from hydrogen peroxide and UV light. Even if their process is highly
active, it has some issues: High consumption of hydrogen peroxide, need of a
strict pH regulation, UV light maintenance etc. A new photocatalytic material
based on hydrogen-treated WO3 nanorods decorated with TiO2 nanoparticles
is presently designed and investigated as an alternative of the homogeneous
catalyzed process. Heterogeneous photocatalysis uses no chemical agents,
works at a large pH range and can be conducted by solar irradiation. The use
of this material could resolve some issues that the company Exp Inc. is
bearing with their current commercialized advanced oxidation process. The
main challenge relies on the design of a highly active catalyst with a low cost
synthesis pathway. Working with Exp. will lead to the development of a
material directly designed to be used in a commercial environment.
P-56
Single-Site Comparison of Prochiral Steering by Different Chiral Modifiers
Jean-Christian Lemay, Peter McBreen
Département de chimie, Université Laval
Stereoselective catalytic sites on achiral metallic surfaces may be prepared by
adsorbing optically active compounds described as chiral modifiers. A
fundamental understanding of the stereodirecting forces in such systems is
necessary to develop more efficient enantioselective catalysts. We will
compare data relating to the chirality transfer complexes formed by the chiral
modifier (R)-(+)-1-(1-naphthyl)ethylamine ((R)-NEA) and its modified
derivative (1R)-1-(8-methyl-1-naphthyl)ethylamine ((R)-8Me-NEA) with the
prochiral substrate 2,2,2-trifluoroacetophenone (TFAP) on Pt(111). Timelapsed scanning tunneling microscopy (STM) allowed us to isolate individual
chiral modifier/substrate complexes at various temperatures. Prochiral
steering on chirally modified Pt(111) was followed with submolecular
resolution, thus enabling conformational, regiospecific and enantiospecific
characterization [1]. Apparent tracking of individual TFAP molecules in
complexes was performed in variable temperature time-lapsed experiments.
An accelerated data extraction method was used to collect STM information
on the geometry of complexes formed and their evolution [2].
References:
[1] Demers-Carpentier, V., et al., Science (2011): 776-780.
[2] Groves, M. N., G. Goubert, A. M. H. Rasmussen, Y. Dong, J-C. Lemay, V.
Demers-Carpentier, P. H. McBreen, and B. Hammer. Surf. Sci. 629 (2014): 4856.
P-57
An Efficient, Biomimetic Synthesis of Lignan Natural Products Via Oxidative
Cyclobutane Fragmentation
Anna Albertson, Jean-Philip Lumb
Lignans comprise a vast array of highly oxygenated, polyaromatic natural
products with important biological activities. Despite their significant
structural diversity, the biosynthesis of lignans begins with the oxidative
coupling of simple propenyl phenols. Attempts to mimic the biosynthetic
coupling of such phenols have suffered from poor regio- and
chemoselectivity. Recently, we demonstrated a novel method of accessing
both furan and furanofuran lignans, utilizing the oxidative ring-opening of a
cyclobutane. Here, we present the extension of this strategy to the synthesis
of aryl tetralin and cyclooctadiene natural products.
P-58
Influence of steam addition in carbonator/calciner on the CO2 capture
performance of Ca9Al6O18-CaO sorbent
Marziehossadat Shokrollahi Yancheshmeh, Hamid R. Radfarnia,
Maria C. Iliuta*
Université Laval, Department of Chemical Engineering
1065, av. de la Médecine Université, QC, Canada G1V 0A6
[email protected]; [email protected]; [email protected]
Calcium looping process is a developing technology for CO2 capture at high
temperatures. Since steam is typically present in gas streams used in the
carbonator and calciner, the influence of steam during carbonation and
calcination should be investigated. In this study, the influence of steam
present during either carbonation or calcination on the capture performance
of a synthetic sorbent was studied. Al-stabilized CaO-based sorbent
containing 78 wt.% CaO and 22 wt.% Ca9Al6O18 was synthesized by a new
method developed in our laboratory (limestone acidification and wet mixing
techniques coupled with two-step calcination). The performance of the
developed sorbent under steam addition in either carbonation or calcination
steps was investigated during 10 cycles of carbonation/calcination. The
experimental results revealed that the presence of steam in carbonator and
calciner (partial pressure of steam = 0.023 bar) increased the CO2 capture
capacity by 106 and 19 %, respectively.
P-59
Non-covalent immobilization of a cofactor-dependent enzyme on iron oxide
magnetic nanoparticles for organic synthesis reactions
Atieh Bahrami, Alain Garnier, Faical Larachi and Maria C. Iliuta*
[email protected];
[email protected]; [email protected];
[email protected]
Cofactor-dependent enzymes play key roles in many organic synthesis
reactions. Large-scale application of enzymes is restricted because of lack of
long term operational stability and their difficult recovery and reuse. To avoid
these drawbacks, research has been carried out on enzyme immobilization.
Binding to a support as physical attachment has the advantage of reversibility
and possibility of high retention of enzyme activity in comparison with
covalent attachment. The use of magnetic nanoparticles (MNPs) for enzyme
immobilization offers many advantages due to their unique size (smaller than
100 nm), high surface area to volume ratio, special magnetic behavior, and
high dispersibility in various solvents. The enzyme immobilized on MNPs
could be simply separated and recycled. This research focuses on noncovalent immobilization of a cofactor-dependent enzyme onto magnetic
nanoparticles, for application in enzymatic catalytic processes.
P-60
Highly pure hydrogen production by integrated sorption-enhanced steam
methane reforming process
Hamid R. Radfarnia and Maria C. Iliuta*
[email protected]; [email protected]
The sorption-enhanced steam methane reforming (SESMR), an integrated
process involving catalytic reaction and in-situ CO2 removal, was investigated
in a fixed bed reactor, highlighting the effect of key operating parameters on
the process performance. Al-stabilized CaO-Ni hybrid sorbent-catalysts with
various nickel loadings (12, 18 and 25 wt% NiO) were developed and tested in
cyclic operation. It was concluded that the proposed hybrid sorbent-catalyst
with NiO loading of 25 wt% led to the best performances: (i) CaO molar
conversion is 41.2% at the end of the 25th sorption cycle and (ii) average CH4
conversion and H2 production efficiency during 10 SESMR cycles are
remarkable (99.1% and 96.1%, respectively). This integrated process was
shown to offer a promising alternative for single-stage production of high
purity hydrogen.
P-61
CO2 separation in flat sheet membrane contactors
Francis Bougie, Ion Iliuta and Maria C. Iliuta*
Département de Génie Chimique, Université Laval
[email protected]; [email protected];
[email protected]
The absorption is a common process in chemical engineering and it is largely
applied in the industrial acid gas treatment and environmental protection. As
an alternative to packed columns, the membrane contactors offer large and
stable gas-liquid contact area reducing the contactor size and weight, as well
as high modularity and easy scale-up. In this work, a new multi-flat-sheet
membrane contactor (FSMC) was developed and used to investigate CO2
removal from CO2/N2 gas mixture using aqueous 2-amino-2-hydroxymethyl1,3-propanediol (AHPD) solution in the presence and the absence of
piperazine (Pz) as activator. Pz activated AHPD solution showed better
performance than single AHPD solution. A two-scale model was developed to
describe the comportment of the multi-flat-sheet membrane contactor.
P-62
Catalyzing the Aerobic Oxygenation of Phenols: A Biomimetic Mechanism.
Mohammad S. Askari,1 Kenneth V.N. Esguerra2, Jean-Philip Lumb,2
Xavier Ottenwaelder*1
<[email protected]>
1 Department of Chemistry and Biochemistry, Concordia University,
Montreal, QC, H4B 1R6
2 Department of Chemistry, McGill University, Montreal, QC, H3A 2K6
Conversion of abundant phenols into o-quinones using copper-catalyzed
aerobic oxidation offers an attractive and green method for the
functionalization of organic molecules. Following the reported Cu(I)-catalyzed
aerobic oxidation of phenols by Lumb [1], we studied the mechanism of O2
activation and phenol oxygenation at low temperatures by stopped-flow UVVis spectroscopy. Our results indicate the activation of O2 by two Cu(I)
centres forming the side-on peroxo complex followed by oxygen-atom
transfer onto a bound phenolate. This mechanism is similar to that of the Cucontaining tyrosinase enzyme, which oxygenates tyrosine into dopaquinone
in the first step of melanogenesis. This similarity explains the high selectivity
of the Lumb conditions for oxygenation, as opposed to radical pathways.
[1] K. V. N. Esguerra, Y. Fall, J.-P. Lumb, Angew. Chem. Int. Ed. 2014, 53, 58775881.
P-63
Mechanism of Catalytic Aerobic Oxygenation of Disubstituted Phenols
Yuxuan Li,1 Mohammad S. Askari,1 Jean-Philip Lumb,2 Xavier
Ottenwaelder*,1
<[email protected]>
The aerobic oxidation of phenols into ortho-quinones is often accompanied
by C-C coupling side-products due to the formation of phenoxyl radicals.
Metalloenzymes and in particular tyrosinase avoid the formation of sideproducts by confining the oxygen-atom-transfer in the first coordination
sphere. Only recently a fully selective oxygenation of disubstituted phenols
using a Cu catalyst was reported [1]. The purpose of this study is to
understand the mechanism of the oxygenation of 3,5-di-tert-butylphenol by
identifying intermediates involved in the reaction by UV-Vis spectroscopy and
control experiments. We here show how the 3,5 disubstitution steers the
reaction towards oxygen-atom transfer, whereas 2,4-disubstituted substrates
undergo radical couplings [1].
[1] Esguerra, K. V. N.; Fall, Y.; Petitjean L.; and Lumb, J. P. J. Am. Chem. Soc.
2014, 136, 7662-7668.
P-64
Bioinspired Phenol Functionalization with Air-Stable Cu Complexes
Laura. A. Rodríguez-Solano,1 Mohammad S. Askari,1 Andrew Proppe,1
Bryony McAllister,1 Jean-Philip Lumb,2 Xavier Ottenwaelder*,1
<[email protected]>
Dioxygen is an ideal oxidant since the by-product of its reduction is water.
However, its oxidative potential is underused in synthetic chemistry because
of activation and selectivity issues. Similarly, despite being abundant, phenols
are underused in synthesis because they readily undergo radical-based
pathways that deter from reaction selectivity. The first copper-catalyzed
process that cleanly controls aerobic oxidation of phenols to selectively
generate o-quinones or catechols was reported by Prof Lumb from McGill [1].
It employs a Cu(I) precatalyst, which requires careful reaction set-up under
inert conditions. We have extended this reactivity to air-stable Cu(II)
complexes, which maintain the selectivity of the reaction while eliminating
the need for inert atmosphere during reaction set-up [2]. This reaction and its
mechanism resembles the reactivity of the metalloenzyme tyrosinase.
[1] Esguerra, K. V. N.; Fall, Y.; and Lumb, J. P. Angew. Chem., Int. Ed. 2014, 53,
5877.
[2]Askari, M. S., Rodríguez-Solano, L. A.; Proppe, A.; McAllister, B.; Lumb, J.P.
and Ottenwaelder, X. Dalton Trans. 2015, DOI: 10.1039/C5DT00822K.
P-65
Structural analysis and molecular dynamics of the self-sufficient P450
CYP102A1: A combined computational/experimental approach to increase
the efficiency of biocatalyst engineering.
Maximilian Ebert1,4, Brahm Yachnin2,4, Guillaume Lamoureux3,4, Albert
Berghuis2,4, Joelle Pelletier1,4
(1Université de Montréal, 2McGill University, 3Concordia University, 4PROTEO)
P450s catalyze the oxidation of non-activated carbon atoms, which is
chemically demanding. Members of the CYP102 family are termed “selfsufficient P450s”, meaning that they contain all the machinery necessary to
ensure the electron transfer and active site regeneration in one single
protein. However, the macromolecular assembly remains unknown. Here we
report results of SAXS analysis that bring new insights into the formation of
the active complex.Predictions of differences in substrate incorporation and
product release from the active site were computed using the adaptive
biasing force (ABF) method. With this pioneering application of ABF in
enzyme engineering, we were able to predict all known important residues
for fatty acid substrate binding in CYP102A1, as well as two additional
residues which were identified and analyzed in vitro to support the in silico
finding. This newly developed computational biology approach, in addition to
conformational studies, will help to guide directed evolution efforts towards
the oxidation of non-native substrates.
P-66
One-Pot Peptide and Protein Chemoenzymatic Conjugation: Combination of
Transamination and Click Chemistry
Rachel, N.M., Pelletier, J.N.
Transglutaminases are enzymes known for their capacity to catalyze protein
cross-linking via the formation of isopeptide amide bonds, by accelerating
acyl-transfer between the γ-carboxamide group of a glutamine substrate, and
the ε-amino group of a lysine substrate. They have also been successfully
used to incorporate a variety of chemical probes, fluorescent or otherwise,
into peptides, proteins, nucleic acids and even tumor cells. We and others
have determined that microbial transglutaminase (MTG) can use a wide
range of synthetic amine-containing compounds as substrates (Gundersen et
al., 2014), ultimately broadening its scope for the modification of glutaminecontaining peptides and proteins. It has also been reported that the MTG
conjugation reaction can be run stepwise, in one pot, with the copper
catalyzed azide-alkyne Huigsen cycloaddition (CuAAC) (Oteng-Pabi et al.,
2014). In order to further expand the scope for MTG-catalyzed fluorescent
protein labeling, we examine two approaches. First, we present a detailed
characterization of this one-pot chemoenzymatic reaction, using both
peptide and protein glutamine donor substrates, and alkyne- or azide-based
amine substrates. Both reactions proved to be compatible under certain
conditions only and could result in yields of over 90% under high reaction
control. These findings highlight the potential to use transglutaminases as a
tool for peptide and protein modification.
P-67
Copper complexes of sulfonated diketimine ligands
Valerie Hardouin Duparc, Frank Schaper*
Centre in Green Chemistry and Catalysis, University of Montreal, Department
of Chemistry, C. P. 6128 Succ. Centre-Ville, Montréal, QC, H3C 3J7, Canada. Email: [email protected]
Over the years, there has been an increased interest in biodegradable plastics
such as PLA. The research on the polymerisation of lactide finds industrial and
academic interest, since until now no catalyst combines good stereocontrol,
high stability, high activity and good polymer weight control. Our group has
reported highly active Cu(II) diketiminate complexes for lactide
polymerisation with a high activity. Despite their high activity, these
complexes did provide excellent polymer weight control and did not show
any tendency to undergo side reactions, such as transersterification or
epimerization. However, Cu(II) diketiminate ligands are highly labile towards
protic substrates. Although stability in the presence of excess alcohol was
demonstrated, presence of water or lactic acid as commonly encountered in
unpurified monomer, as well as exposure to ambient atmosphere led to
catalyst decomposition.
-diketimine ligands and their copper
complexes as potential air- and moisture-stable catalysts for lactide
polymerization. We present first synthetic results and initial explorations of
their stability and reactivity in lactide polymerization.
P-68
Lactide polymerization using air-stable Manganese alkoxide complexes
Pargol Daneshmand Kashani, Frank Schaper*
Centre in Green Chemistry and Catalysis, University of Montreal, Department
of Chemistry, C. P. 6128 Succ. Centre-Ville, Montréal, QC, H3C 3J7, Canada. Email: [email protected]
While a large number of well defined catalysts for cyclic ester polymerization
are known, they are for the most part sensitive to oxygen or water, which
limits their potential application and requires intensive purification of the
monomer. We investigated the preparation of more chemically robust
catalysts which contain non-oxidizable metal centers and ligands stable
against protonation. To retain high polymerization activity, we further require
an alkoxide group for fast initiation and an open coordination site for
monomer coordination. For toxicity and economic reasons, the metal center
should be a first-row transition metal and the ligand limited to nitrogen and
oxygen as heteroatoms.
Manganese(III) complexes containing dianionic tetradentate bisphenolate
ligands are potential candidates for such air-stable polymerization catalysts.
We thus prepared several complexes of the general formula L4MX, where
“L4” represents the diphenolate ligand and X is either methoxide or chloride.
The complexes were investigated for lactide polymerization following a
Lewis-acid activation mechanism (X = Cl) or a coordination-insertion
mechanism (X = OR). The catalysts proved to be moderately active at
polymerizations in molten monomer. Even at these high temperatures,
polymerization was possible using unpurified monomer, indicative for
increased catalyst stability.
P-69
Effects of polymetal sulphides galvanic interactions on ore conditioning and
flotation
DFT simulations and packed-bed electrochemical reactor studies
Olivier Gravel, Amin Sarvaramini, Dariush Azizi, Muhammad Khalid, Brian
Hart, Faïçal Larachi
In today’s global economy, Québec’s mining industry must continually find ways to
increase its productivity and profitability to remain globally competitive. In this regard,
flotation is one of the most critical processes in the mining industry. Its fundamentals
involve numerous and complex reactions, all of which affect metallurgical performances.
For process optimization, ore variability makes it difficult to rapidly diagnose chemistry
related problems using traditional metallurgical approaches. The process chemistry
operative is controlled, in large part, by the interaction of the ore’s constituent minerals
and the various reagents added to the system to promote flotation selectivity. The effect
of this interaction is mineral surface chemistry modification, which translates into
performance variability in flotation and metal recovery.
Therefore, inscribed in a much larger project on the application of Advanced Surface
Characterization Technologies, the present project uses the innovative packed-bed
electrochemical reactor (PBER) concept developed in the group coupled with microflotation tests and density functional theory (DFT) simulations to allow for a novel
assessment of the impacts of galvanic interactions on mineral oxidation, activation,
passivation and collector attachment towards identification of positive outcome testing
parameters that could result in process selectivity or recovery improvements in flotation
processes.
The experimental results show specific effects trends emerging from copper and lead
activation as well as collector attachment in multilayer multisulphide model systems
composed of sphalerite, chalcopyrite, pyrite and galena in different configurations to
enable or disable anodic/cathodic galvanic interactions among the constituents. DFT
simulations, for their part, shed new light on our understanding of the interaction of the
aerophine collector with lead-activated and pure sphalerite in ore separation scenarios.
They also demonstrate the necessity of including the interaction energetics of water
molecules with the solid interfaces to be activated as part and parcel of the ensemble of
phenomena in order to arrive to sound simulation conclusions.
P-70
Utility of Protected Sulfones for Regioselective C-H Activation
Fei Chen and Pat Forgione*
Department of Chemistry & Biochemistry, Concordia University, Montréal,
QC, H4B 1R6 and Centre in Green Chemistry and Catalysis, Montreal, QC
[email protected]
As carbon-carbon (C-C) bonds are the essential bond in nature, reactions that form C-C bonds, are
always of interest in organic chemistry. C-C bonds that connect two aromatic systems are typically
formed through palladium-catalyzed coupling reactions, such as Suzuki, Negishi and Stille
reactions. In the last decade, green chemistry has become increasingly important and greener
modern palladium-catalyzed C-H activation, decarboxylative cross-coupling and desulfinative
cross-couplings have attracted increased attention. Desulfinative cross-coupling are less utilized as
the starting materials are mainly salts and therefore limit the versatility of these cross-coupling in
organic synthesis despite advantages such as high yields and regioselectivity. To overcome this
problem we are developing protecting groups such as sulfonylated pyridines (Scheme 1) or
pyrimidines, where the hetero-aromatic systems can be easily installed and removed through SNAr
reactions.1–3 The nitrogen contained hetero-aromatics can also act as directing group in
functionalizing the ortho position and subsequently removed to reveal the sulfinate moiety for
further transformation.
Scheme 1: Proposed protecting group installation and deprotection with its potential directing
function.
(1)
Yuan, Y.; Guo, S. Synlett 2011, 2011, 2750–2756.
(2)
Maloney, K. M.; Kuethe, J. T.; Linn, K. Org. Lett. 2011, 13, 102–105.
(3)
Gianatassio, R.; Kawamura, S.; Eprile, C. L.; Foo, K.; Ge, J.; Burns, A. C.; Collins, M. R.; Baran,
P. S. Angew. Chem. Int. Ed. 2014, 53, 9851–9855.
P-71
Iron catalyzed asymmetric oxidation of sulfides using
hydrogen peroxide
Angela Jalba and Thierry Ollevier*
Département de chimie, Pavillon Alexandre-Vachon, Université Laval, 1045
avenue de la Médecine, Québec (Québec) G1V 0A6. E-mail:
[email protected]
Chiral sulfoxides are important compounds, which find increasing use as
chiral synthons in organic synthesis for the preparation of biologically active
compounds or as chiral ligands in enantioselective catalysis. The asymmetric
oxidation of sulfides using chiral metal catalysts and H2O2 is one of the best
ways to prepare enantio-enriched sulfoxides because these oxidizing systems
can generally be applied to a wide range of substrates, and only a catalytic
amount of the metal complex is necessary. C2 symmetrical bis(oxazolinyl)bipyridine chiral ligand, used with FeX2 and H2O2, was found to be
very effective in the asymmetric oxidation of aromatic sulfides. The synthesis
and the application of such systems for the asymmetric oxidation of
thioanisole will be presented.
P-72
Self-metathesis route to functionalized monomers from methyl oleate for
biopolymers production using rhenium-based alumina-supported catalyst
Abdelnasser Abidli*1, 2 and Khaled Belkacemi1, 2
1
Department of Soil Sciences and Agri-Food Engineering, Laval University. G1V 0A6,
Quebec city, Quebec, Canada. 2Centre in Green Chemistry and Catalysis (CGCC). H3A 0B8,
Montreal, Quebec, Canada.
E-mail: [email protected]; Tel: (581) 777-0860
Catalytic metathesis reaction is a powerful tool allowing access to a variety of symmetrical
and asymmetrical monomers. After demonstrating that methyltrioxorhenium (MTO)
supported on zinc chloride-modified wormhole-like conventional alumina is a suitable
catalyst for the metathesis of bulky functionalized substrates including methyl oleate 1, 2
and triolein.3 In the present work, we show that well-hexagonal ordered mesoporous
alumina (OMA), having a well-arranged cylindrical mesoporous network and uniform pore
size distribution is a suitable catalytic support for shape-selective catalysis. Similarly, MTO
was supported on zinc chloride-modified OMA, this new catalyst design is offering several
advantages including metathesis reaction rate enhancement through better mass transfer
phenomena. Also, compared to wormhole-like alumina-based MTO catalyst, improved
selectivity towards desired methyl oleate self-metathesis products was obtained using the
OMA supports.4, 5 The synthesized bio-based symmetrical monomers are interesting
building blocks for the preparation of bio-based polymers. Such green polymers are highly
desired as suitable alternatives to conventional polymers having a low environmental
impact. These bioplastics are used in various applications including food packaging,
biomedical tools, electronic devices, bags, automobile industry, etc.
Keywords: Bioplastics; functionalized monomers; OMA; renewable resources; MTO
References
1.
S. K. Pillai, S. Hamoudi and K. Belkacemi, Appl. Catal., A, 2013, 455, 155-163.
2.
S. K. Pillai, S. Hamoudi and K. Belkacemi, Fuel, 2013, 110, 32-39.
3.
S. K. Pillai, A. Abidli and K. Belkacemi, Appl. Catal., A, 2014, 479, 121-133.
4.
A. Abidli, S. Hamoudi and K. Belkacemi, Dalton Trans., 2015, DOI: 10.1039/C4DT03630A.
5.
A. Abidli, S. K. Pillai, S. Hamoudi and K. Belkacemi, XXI International Conference on
Chemical Reactors (CHEMREACTOR-21) September 22-25, Delft, The Netherlands. ISBN 978-5906376-06-0, 2014, 184-185.

Centre in Green Chemistry and Catalysis - CCVC

Transcription

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