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Program - CCROS – Catalysts and Catalytic Reactions for Organic
7th Annual PhD Workshop of the International Research Training Group GRK1038 Program July 25th to 25th, 2013 University of Freiburg Großer Hörsaal Chemie Welcome Welcome to our 7th annual PhD Workshop here in Freiburg! In this Guide you will nd the important information about and around the following next two days including the scientic program and the get together. Content Program General Informations Maps List of Participants Abstracts Notes We thank Syngenta for their kind supply of note pads and pens. 1 2 Program Program Wednesday, 24th of July 2013 1230-1300 Registration and Get together Foyer in front of lecture hall 1300-1305 Welcome and Opening Remarks Großer Hörsaal Chemie 1305-1315 Welcome speach by Prof. Dr. Bernhard Breit 1315-1445 Lectures - Session 1 13 -13 Max Hofferberth ALU Freiburg, Prof. Dr. Reinhard Brückner Total Synthesis of α- and β-Lipomycin: Application of a Highly Convergent and adaptable Double Stille-Coupling 15 45 1345-1415 Ingo Schnapperelle TU München, Prof. Dr. Thorsten Bach C4 Selective Arylation of Thiophenes by Oxidative C-H Activation 1415-1445 Sarah Fernandez LMU München, Prof. Dr. Paul Knochel Chromonium-Catalyzed sp2-sp2 Cross-Coupling Reactions 1445-1515 Coffee Break Foyer in front of lecture hall 1515-1615 Lectures - Session 2 1515-1545 Urs Gellrich ALU Freiburg, Prof. Dr. Bernhard Breit Mechanistical Studies of the Rhodium Catalyzed Hydroformylation with SelfAssembling Ligands 1545-1615 Robert Kastl ETH Zürich, Prof. Dr. Helma Wennemers Peptide-catalyzed Stereoselective Conjugate Addition Reactions Generating AllCarbon Quaterny Stereogenic Centers 1615-1645 Coffee Break Foyer in front of lecture hall 1645-1745 Lectures - Session 3 1645-1715 Plamen Bichovski ALU Freiburg, Dr. Jan Streuff Titanium Catalyzed Redox-Umpolung Reactions 1715-1745 Richard Brimioulle TU München, Prof. Dr. Thorsten Bach Enantioselective [2+2] Photocycloadditions Catalyzed by Chiral Oxazaborolidine Based Lewis Acids 1745-1800 Short Break (sorry no coffee) Foyer in front of lecture hall / outside 3 1800-1920 Evening Lecture 1800-1920 Evening Lecture Prof. Dr. Peter Hofmann University of Heidelberg Bulky, Electron-Rich, Small Bite-Angle Ligands: Organometallic Chemistry for Homogeneous Catalysis 1930- open end Dinner Restaurant „Harmonie“, more information see page xy Thursday, 25th of July 2013 0900-0915 Get together 0915-0945 Lectures - Session 4 0915-0945 Nico Santchi ETH Zürich, Prof. Dr. Antonio Togni Mechanistic Insights into Generation of CF 3-Radicals from Hypervalent Iodine Reagents 0945-1015 Annette Frischmuth LMU München, Prof. Dr. Paul Knochel The Copper-mediated Intramolecular Carbomagnesiation - A new Approach to Indoles and Azaindoles 1015-1045 Laetitia Souillart EPF Lausanne, Prof. Dr. Nicolai Cramer Exploiting Rh(I)-Rh(III) Cycles in Enantioselective Strain-promoted C-C Bond Cleavages 1045-1115 Coffee Break Foyer in front of lecture hall 1115-1315 Lectures - Session 5 1115-1145 Marc-André Müller University of Basel, Prof. Dr. Andreas Pfaltz Asymmetric Hydrogenation of α, β-Unsaturated Nitriles Using Chiral Iridium N,P Ligand Complexes 1145-1215 Uwe Jakob ALU Freiburg, Prof. Dr. Willi Bannwarth An Orthogonal Protection Scheme for Carboxylic Acids Based On the Metal Ion Induced Cleavage of Chelating Amides 1215-1220 Closing Remarks and Goodbye 1225-1230 Group picture 1230 Lunch „Mensa Institutsviertel“, more information see page xy 4 General Information General Information Scientic Sessions Hotels The talks will be given in English. The oral presentation of the PhD presentations will last 20 minutes followed by the discussion. The evening lecture will be given by Prof. Dr. Peter Hofmann from the University of Heidelberg. Location Großer Hörsaal Chemie Faculty for Chemistry and Pharmacy University of Freiburg Albertstraße 21 | 79104 Freiburg Description A When entering the chemistry building from the main entrance continue straight through the foyer, climb the stairs and turn to the left. You should now pass our library with hart working students. Follow the corridor and step down the stairs. Here you should nd us standing in the hall, welcoming you with your name badge. B When entering from the west side, you are standing directly in the mentioned hall. Hotel Atlanta Rheinstraße 29 79104 Freiburg +49 (0)761 296970 www.atlantahotel.de/de/ about 5 min walk to Institute Gästehaus Jacoby Rieselfeldallee 23 79111 Freiburg +49 (0)761 47 64 389 or +49 (0)178 13 30 856 www.gaestehausjacoby.de/ Coffee Breaks Hotel Am Rathaus Rathausgasse 4, 79098 Freiburg im Breisgau +49 (0)761 296160 www.am-rathaus.de/ about 10 min walk to Institute Coffee, tea and cold drinks will be waiting for us outside the lecture hall as well as some cookies for the small hunger. Location Hall in front of Großer Hörsaal Chemie Dinner on Wednesday Evening The event is meant to stimulate the exchange between the participating universities. After a day of scientic input, we will meet for dinner and enjoy the more informal get-together. Location Restaurant „Harmonie“ in the centre of Freiburg http://www.harmonie-restaurant.de/ Grünwälderstr. 16-18 | 79098 Freiburg | 0761 / 202 56 76 Menu We will have a three-course dinner with starter, main dish and dessert. Four different main dishes (3x meat and 1x vegetarian) will be available. One non-alcoholic drink will be for free. Further drinks (alcoholic or non-alcoholic) have to be paid individually (in €). Parking If you are coming by car, you need a ticket from the university to be allowed to park on the faculty ground. It is 1,50€ per day. Lunch on Thursday Each participant of our conference will receive a food voucher for lunch in Mensa Institutsviertel. This voucher is valid for one soft-drink and “Essen 1”, “Essen 2” or “Schneller Teller”. It is not valid for the buffet. Location Mensa Institutsviertel Stefan-Meier-Str. 28 | 79104 Freiburg Description Leaving the building on the west side, you will nd the Mensa when turning to the right and following the ow of students. Menu Can be found online at: http://www.swfr.de/essen-trinken/speiseplaene/mensa-institutsviertel/ 5 6 Maps List of Participants University of Basel Chemie Atlanta am Rathaus Münster Name Group Email Johanna Auth Pfaltz [email protected] Stefan Gruber Pfaltz [email protected] Patrick Isenegger Pfaltz [email protected] Marc Müller Pfaltz [email protected] Larissa Pauli Pfaltz [email protected] Andreas Pfaltz, Prof. Dr. Pfaltz [email protected] Robin Scheil Pfaltz [email protected] York Schramm Pfaltz [email protected] Chatterjee Anamitra Ward [email protected] Maxime Barnet Ward [email protected] Name Group Email Anika Ahrens Bannwarth [email protected] Uwe Jakob Bannwarth [email protected] Swetlana Scherbakow Bannwarth [email protected] Markus Sterk Bannwarth [email protected] Simon Allmendinger Breit [email protected] ThorstenBeck Breit [email protected] Bernhard Breit, Prof. Dr. Breit [email protected] Lucie Colas Breit [email protected] Stephanie Ganss Breit [email protected] Urs Gellrich Breit [email protected] Amelie Gutmann Breit [email protected] Matthias Kähny Breit [email protected] Alexander Köpfer Breit [email protected] Philipp Koschker Breit [email protected] Adrian Pritzius Breit [email protected] Alexander Straub Breit [email protected] Adrian Pritzius Breit [email protected] Alexander Straub Breit [email protected] Johannes Ullrich Breit [email protected] Sebastian Wünsch Breit [email protected] Kun Xu Breit [email protected] Harmonie University of Freiburg Mensa Chemie Atlanta 7 8 List of Participants Abstracts Name Group Email Thomas Baumann Brueckner [email protected] Johannes Beiche Brueckner [email protected] Reinhard Brückner, Prof. Dr. Brueckner [email protected] Julian Diehl Brueckner [email protected] Tobias Engesser Brueckner [email protected] Thomas Hampel Brueckner [email protected] Max Hofferberth Brueckner [email protected] Michael Kreibich Brueckner [email protected] Markus Neumeyer Brueckner [email protected] David Peter Brueckner [email protected] Simon Ruppenthal Brueckner [email protected] Frank Sartorius Brueckner [email protected] Marc Trebing Brueckner [email protected] Huiji Zhu Brueckner [email protected] Hannes Boehrer Krossing [email protected] Thies Olaf Petersen Krossing [email protected] Miriam Schwab Krossing [email protected] Sabrina Loschonsky Mueller [email protected] Name Group Email Ingo Schnapperelle Bach [email protected] Richard Brimiouelle Bach [email protected] Laetitia Souillart Cramer laetitia.souillart@ep.ch Sarah Fernandez Knochel [email protected] Annette Frischmuth Knochel [email protected] Nico Santschi Togni [email protected] Robert Kastl Wennemers [email protected] Annette Bahlinger Wennemers [email protected] External 9 Max Hofferberth ALU Freiburg, Prof. Dr. Reinhard Brückner Total Synthesis of α- and β-Lipomycin: Application of a Highly Convergent and adaptable Double Stille-Coupling page 11 Ingo Schnapperelle TU München, Prof. Dr. Thorsten Bach C4 Selective Arylation of Thiophenes by Oxidative C-H Activation page 12 Sarah Fernandez LMU München, Prof. Dr. Paul Knochel Chromonium-Catalyzed sp2-sp2 Cross-Coupling Reactions page 13 Urs Gellrich ALU Freiburg, Prof. Dr. Bernhard Breit Mechanistical Studies of the Rhodium Catalyzed Hydroformylation with SelfAssembling Ligands page 14 Robert Kastl ETH Zürich, Prof. Dr. Helma Wennemers Peptide-catalyzed Stereoselective Conjugate Addition Reactions Generating All-Carbon Quaterny Stereogenic Centers page 15 Plamen Bichovski ALU Freiburg, Dr. Jan Streuff Titanium Catalyzed Redox-Umpolung Reactions page 16 Richard Brimioulle TU München, Prof. Dr. Thorsten Bach Enantioselective [2+2] Photocycloadditions Catalyzed by Chiral Oxazaborolidine Based Lewis Acids page 17 Nico Santchi ETH Zürich, Prof. Dr. Antonio Togni Mechanistic Insights into Generation of CF 3-Radicals from Hypervalent Iodine Reagents page 18 Annette Frischmuth LMU München, Prof. Dr. Paul Knochel The Copper-mediated Intramolecular Carbomagnesiation - A new Approach to Indoles and Azaindoles page 19 Laetitia Souillart EPF Lausanne, Prof. Dr. Nicolai Cramer Exploiting Rh(I)-Rh(III) Cycles in Enantioselective Strain-promoted C-C Bond Cleavages page 20 Marc-André Müller University of Basel, Prof. Dr. Andreas Pfaltz Asymmetric Hydrogenation of α, β-Unsaturated Nitriles Using Chiral Iridium N,P Ligand Complexes page 21 Uwe Jakob ALU Freiburg, Prof. Dr. Willi Bannwarth An Orthogonal Protection Scheme for Carboxylic Acids Based On the Metal Ion Induced Cleavage of Chelating Amides page 22 10 C4-Selective Arylation of Thiophenes by Oxidative C-H-Activation Total Synthesis of - and -Lipomycin: Application of a Highly Convergent and Adaptable Double STILLECoupling Strategy for the Synthesis of 3-(Polyenoyl)tetramic Acids Ingo Schnapperelle and Thorsten Bach* Lehrstuhl für Organische Chemie I and Catalysis Research Center (CRC), Technische Universität München, Lichtenbergstr. 4, Garching, D-85747, Germany Max Hofferberth and Reinhard Brückner* Email: [email protected] - web page: http://www.oc1.ch.tum.de/home_en/ Institut für Organische Chemie, Albert-Ludwigs-Universität, Albertstraße 21, 79104 Freiburg, Germany; e-mail: [email protected] 3-( -Hydroxymethylidene)pyrrolidine-2,4-diones constitute the major tautomer of structures Compounds in which define a class of natural products, which continues to evoke interest both in the synthetic[1] and biosynthetic community[2]. For the synthesis of biaryl compounds, transition metal-catalyzed cross-couplings of aryl(pseudo)-halides are usually the method of choice. Nevertheless, tremendous efforts have been made during the last decade in the field of palladium-catalyzed C-H activation, no longer requiring prefunctionalization of at least one reaction partner. [1] More recently this concept has been applied for the functionalization of heteroaromatics. [2] In this respect an additional challenge has to be considered as regioselctivity becomes important, which is in many cases determined by the inherent reactivity of the heterocycle.[3] Under optimized conditions, monosubstituted as well as disubstituted thiophenes undergo a facile and regio selective oxidative coupling reaction at carbon atom C4. [4] This uncommon selectivity was observed with various aryl boronic acids as nucleophiles in the presence of silver oxide (2.0 equiv.), cesium trifluoracetate (tfa) (1.0 equiv.), benzoquinone (BQ) (0.5 equiv.) and catalytic amounts of Pd(tfa)2 (10 mol%) employing mixtures of trifluoroacetic acid (TFA) and acetic acid (AcOH) as the solvent. Recently other groups[5,6] carried out mechanistic investigations based on computational calculations aiming towards the elucidation of the catalytic cycle for the C4-selective arylation of thiophene derivatives. Unfortunately, previously reported reaction conditions differ substantially from those shown above. Therefore we decided to carry out mechanistic experiments to obtain mechanistic insights and an explanation for the observed selectivity. We have synthesized a prototypical (polyenoyl)tetramic acids, namely -lipomycin,[3] employing a novel approach, which is variable and convergent. In this approach a very useful Distannane-buildingblock was utilized.[4] Furthermore, we have proven the, previously unknown, -lipomycin by chiral chromatography of its degradation products. [1] R. Schobert, A. Schlenk, Bioorg. Med. Chem. 2008, 16, 4203-4221 and literature cited therein. [2] E. g.: C. Bihlmaier, E. Welle, C. Hofmann, K. Welzel, A. Vente, E. Breitling, M. Müller, S. Glaser, A. Bechthold, Antimicrob. Agents Chemother. 2006, 50, 2113-2121. [3] B. Kunze, K. Schabacher, H. Zähner, A. Zeeck, Arch. Mikobiol. 1972, 86, 147-174. [4] First synthesis and applications A. Sorg, R. Brückner, Angew. Chem. 2004, 116, 4623-4626; Angew. Chem. Int. Ed. 2004, 43, 4523-4526; J. Burghart, R. Brückner, Eur. J. Org. Chem. 2011, 150-165; J. Burghart, A. Sorg, R. Brückner, Chem. Eur. J. 2011, 17, 6469-6483. 11 1 X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem. 2009, 121, 5196-5217; Angew. Chem. Int. Ed. 2009, 48, 5094-5115. 2 J. Roger, A. L. Gottumukkala, H. Doucet, ChemCatChem 2010, 2, 20-40. 3 L.-C. Campeau, M. Bertrand-Laperl, J.-P. Leclerc, E. Villemure, S. Gorelsky, K. Fagnou, J. Am. Chem. Soc. 2008, 130, 3276-3277. 4 I. Schnapperelle, S. Breitenlechner, T. Bach, Org. Lett. 2011, 13, 3640-3643. 5 M. Steinmetz, K. Ueda, S. Grimme, J. Yamaguchi, S. Kirchberg, K. Itami, A. Studer, Chem. Asian. J. 2012, 7, 1256-1260. 6 S.-Y. Tang, Q.-X. Guo, Y. Fu, Chem. Eur. J. 2011, 17, 13866-13876. 12 Mechanistical studies of the Rhodium Catalyzed Hydroformylation with Self Assembling Ligands Urs Gellrich, Bernhard Breit* Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104 Freiburg, Germany E-mail: Webpage: [email protected] http://www.breit-group.uni-freiburg.de/ Selectivity control in homogeneous metal complex catalysis is most frequently achieved by crafting the microenvironment of the catalytically active metal center upon binding of appropriate ligand architectures to the metal center. Among the many ligands used, bidentate ligands occupy an important position. During the last years our group was able to successfully develop self-assembling ligands, interacting via hydrogen bonds.[1] In order to improve catalytic reactions and ligands it is by all means necessary to completely understand the nature of the catalytically active species. Hence, online monitoring of progressing catalytic transformations, supported by quantum mechanical calculations, can deliver valuable informations on the intermediates involved in catalysis. We herein report on our insights into hydroformylation reactions with the 6-DPPon ligand using online ReactIRTM and NMR-spectroscopy together with QM-calculations.[2,3] Figure 1: Direct observation of the formation of an intermediate of the catalytic cycle and the corresponding DFT calculated structures. 13 (1) W. Seiche, B. Breit, J. Am. Chem. Soc. 2003, 125, 6608. (2) U. Gellrich, J. Huang, W. Seiche, M. Keller, M. Meuwly, B. Breit J. Am. Chem. Soc. 2011, 133, 964. (3) U. Gellrich, W. Seiche, M. Keller, B. Breit, Angew. Chem. 2012, 124, 11195; Angew. Chem. Int. Ed. 2012, 51, 11038. 14 15 16 17 18 The copper-mediated intramolecular carbomagnesiation – A new approach to indoles and azaindoles A mild and general intramolecular copper-mediated carbomagnesiation procedure for the synthesis of functionalized indoles as well as 4-, 5-, 6-, and 7-azaindoles starting from the readily available ynamides. Subsequent reaction with various electrophiles (acid chlorides, allylic bromides) provides polyfunctional Nheterocycles in good yields. Features of this method: Practical synthesis of the ring closing precursors: Straightforward access to highly functional indoles starting from readily available ynamides: Expeditive synthesis of 7-azaindoles: Expeditive synthesis of 5-azaindoles: Selective synthesis of 4- or 6-azaindoles from the same precursor: 19 20 Asymmetric Hydrogenation of An Orthogonal Protection Scheme for Carboxylic Acids Based On the Metal Ion Induced Cleavage of Chelating Amides -Unsaturated Nitriles Using Chiral Iridium N,P Ligand Complexes Uwe Jakob, Stephan Mundinger and Willi Bannwarth Marc-André Müller,1 and Andreas Pfaltz1* Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg Albertstraße 21, 79104 Freiburg, Germany 1 Department of Chemistry, University of Basel St. Johanns-Ring 19, CH-4056 Basel, Switzerland *Corresponding author; e-mail: [email protected] Asymmetric hydrogenation is one of the most commonly applied reactions to generate enantiomerically enriched molecules from prochiral starting materials.1 In particular, iridiumbased catalysts showed high applicability in the hydrogenation of substrates bearing no or only weakly coordinating groups attached to the double bond. 2 On the other hand, strongly coordinating functional groups, such as nitriles, are frequently observed as inhibitors of iridium-based catalysts.3 In most cases, the preparation of complex organic molecules entails the need to apply protecting groups. When such groups are applied to multistep synthesis basic requirements are straightforward insertion, robustness to different reaction conditions and selective cleavage, preferably with high yields and under mild conditions. In addition, a cleavage step orthogonal to that used for common protecting groups would also be desirable [1]. O MeOH O R1 OH O N 1.) protection N 2.) modification R2 NH N R2 MX2 N N M X X N O Ba(OH)2 x 8 H2O MeOH 4a-c The fact that nitriles are important functional groups in different research areas highlights the demand for easily accessible enantiomerically enriched molecules containing this group. By modifications of “standard reaction conditions” we were able to find an easy applicable protocol for the asymmetric hydrogenation of this kind of substrates. Herein, we give an overview on this transformation, providing a detailed insight into the substrate scope and discussing important parameters of this reaction. REFERENCES: 1. 2. 3. 4. R. Noyori, Angew. Chem. Int. Ed. 2013, 52, 79. D. H. Woodmansee, A. Pfaltz, Chem. Commun. 2011, 47, 7912. D. H. Woodmansee, M.-A. Müller, M. Neuburger, A. Pfaltz Chem. Sci. 2010, 1, 72. a) R. A. Michelin, M. Mozzon, R. Bertanix Coord. Chem. Rev. 1996, 147, 229; b) F. F. Fleming, Nat. Prod. Rep. 1999, 16, 597; c) V. L. Rao, A. Saxena, K. N. Ninan, J. Macromol. Sci. C:Polym. Rev. 2002, C42, 513. OMe N O 3.) deprotection N R2 R2 Our new protection scheme for carboxylic acids fulfills all these criteria. The carboxylic acids can be protected as very stable chelating amides. The cleavage reaction can be achieved under mild conditions in the presence of metal ions. Their complexation involves the amide nitrogen which then allows for an attack by weak nucleophiles such as MeOH forming the corresponding methyl esters. Alternatively, the carboxylic acid can be obtained in the presence of Ba(OH)2 x 8 H2O after acidic work up [2, 3]. The cleavage rate depends both on the chelator and on the metal source. This fact makes it possible to develop an orthogonal protection scheme for carboxylic acids based on the attachment of different chelators to the carboxyl functions of a molecule. Since this orthogonal protection scheme has the advantage of mild and selective cleavage reactions it should find widespread application in synthetic organic chemistry. O N O N N O N N N N N N CH3 N CH3 References [1] P. Kocienski, Protecting Groups, 3rd Ed., Thieme, 2003. [2] M. C. Broehmer, S. Mundinger, S. Bräse, W. Bannwarth, Angew. Chem. Int. Ed. 2011, 50, 6175 – 6177. [3] S. Mundinger, U. Jakob, P. Bichovski, manuscript in preparation. 21 OH 22
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