Organo-metal cooperative catalysis ♦ 3rd year seminar Tiffany Piou Supervisors: Dr. Luc Neuville and Prof. Jieping Zhu 25.01.12

Transition metal catalysis One of the most useful and powerful tool in organic chemistry. Examples of transition metal reactions: Cross-coupling Hydroformylation Alkene and alkyne metathesis Hydrogenation Cyclopropanation Hydroamination Hydroesterification Hydrocarboxylation Pauson-Khand reaction Isomerisation of olefins Hydrocyanation Advantages: Chemoselectivity Regioselectivity Stereoselectivity High yield Reproducibility Low catalyst loading Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim, 2nd ed., 2004, vol. 1 and 2.

Organocatalysis Major topic in organic chemistry Access to enantiomerically enriched molecules Explosion of new organocatalysts Main advantages: Not expensive Easily accessible Stable to air and moisture Enantioselective Organocatalysis: Reactions and Experimental Procedure (Ed,: P. I. Dalko), Wiley-VCH, Weinheim, 2007.

Cooperation between transition metal and organocatalyst Concept introduced by Krische in 2003. Combine Morita-Baylis-Hillman type reaction and Tsuji-Trost reaction Use of “non classical” electrophilic partner Open new perspectives B. G. Jellerichs, J.-R. Kong, M. J. Krische J. Am. Chem. Soc. 2003, 125, 7758-7759.

Cooperative catalysis Cooperation between transition metal and organocatalyst New tool in organic chemistry Cooperative catalysis Unprecedented transformations not currently possible with the transition metal or the organocatalyst alone. Problem: compatibility? C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025. Z. Shao, H. Zhang, Chem. Soc. Rev. 2009, 38, 2745-2755.

Two different types of cooperation The two catalysts operate simultaneously The two catalysts operate Successively in a “one pot” fashion C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025. Z. Shao, H. Zhang, Chem. Soc. Rev. 2009, 38, 2745-2755.

Two different types of cooperation The two catalysts operate simultaneously The two catalysts operate Successively in a “one pot” fashion C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025. Z. Shao, H. Zhang, Chem. Soc. Rev. 2009, 38, 2745-2755.

Cooperative Reactions: Brönsted acid/base Aminocatalysis Lewis Base Cooperative Reactions: Transition Metal + Organocatalyst NHC organocatalyst Bifunctional catalyst C. Zhong, X. Shi, Eur. J. Org. Chem. 2010, 2999-3025. Z. Shao, H. Zhang, Chem. Soc. Rev. 2009, 38, 2745-2755.

Transition metal with aminocatalysis Pioneering work by Barbas, List and MacMillan Amine activations are the most studied organocatalytic system Functionnalization of carbonyl compounds One of the most popular strategies in cooperative catalysis S. Mukherjee, J. W. Yang, S. Hoffmann, B. List, Chem. Rev. 2007, 107, 5471-5569.

Intermolecular α-allylation First example, Cordova et al. in 2006, Breit et al. in 2009, No stereoselectivity I. Ibrahem, A. Cordova, Angew. Chem. Int. Ed. 2006, 45, 1952-1956. I. Usui, S. Schmidt, B. Breit, Org. Lett. 2009, 11, 1453-1459.

Intramolecular α-allylation Saicic et al. in 2007, 2009, Chiral amine catalysts tested failed F. Bihelovic, R. Matovic, B. Vulvovic, R. N. Saicic, Org. Lett. 2007, 9, 5063-5066. B. Vulvovic, F. Bihelovic, R. Matovic, R. N. Saicic, Tetrahedron 2009, 65, 10485-10494.

Enamine addition to activated alkyne Multicomponent reaction developed by Wu’s group in 2007, Tandem reaction published by Dixon’s, Q. Ding, J. Wu, Org. Lett. 2007, 9, 4959-4962. T. Yang, A. Ferrali, L. Campbell, D. J. Dixon, Chem. Commun. 2008, 2923-2925.

Enamine induced enantioselective cooperative reaction Nishibayashi et al in 2010, M. Ikeda, Y. Miyake, Y. Nishibayashi, Angew. Chem. Int. Ed. 2010, 49, 7289-7293.

Enamine catalysis with SOMO photoredox catalysis SET = single electron transfer A. Nicewicz, D. W. C. MacMillan, Science 2008, 322, 60-77.

Cooperative Reactions: Brönsted acid/base Aminocatalysis Lewis Base Cooperative Reactions: Transition Metal + Organocatalyst NHC organocatalyst Bifunctional catalyst

Chiral Brönsted-acid/base with metal activated substrates Chiral Brönsted acid/base catalyst: a powerful strategy. In combination with transition-metal, 3 approaches:

Chiral Brönsted-acid/base with metal activated substrates Chiral Brönsted acid/base catalyst: a powerful strategy. In combination with transition-metal, 3 approaches:

Asymmetric Counter-Anion-directed catalysis Strategy (ACDC) First example proposed by Toste et al, G. L. Hamiltion, E. J. Kang, M. Mba, F. D. Toste, Science 2007, 317, 496-499.

Enantioselective α-allylation of aldehyde via ACDC strategy List et al., G. Jiang, B. List, Angew. Chem. Int. Ed. 2011, 50, 9471-9474.

Chiral Brönsted-acid/base with metal activated substrates Chiral Brönsted acid/base catalyst: a powerful strategy. In combination with transition-metal, 3 approaches:

Chiral Brönsted acid activation Asymmetric alkynylation of α-imino esters proposed by Chan et al.: Limited scope! J.-X. Ji, J. Wu, A. S. C. Chan, Proc. Natl. Acad. Sci. USA 2005, 102, 11196-11200.

Chiral Brönsted acid activation: sp carbon nucleophile Rueping et al. 2007, Arndtsen et al., Inexpensive catalyst Large scope Excellent ee M. Rueping, A. P. Antonchick, C. Brinkmann, Angew. Chem. Int. Ed. 2007, 46, 6903-6906. Y. Lu, T. C. Johnstone, B. A. Arnsdtsen, J. Am. Chem. Soc. 2009, 131, 11284-11285.

Chiral Brönsted acid activation: Rh mediated-carbene nucleophile W.-H. Hu, X.-F. Xu, J. Zhou, W.-J. Liu, H.X. Huang, J. Hu, L. P. Yang, L.-Z. Gong, J. Am. Chem. Soc. 2008, 130, 7782-7783.

Enantioselective hydrogenation of imine Beller’s group in 2011, An alternative to the Hantzsch dihydropyridine S. Zhou, S. Fleisher, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 5120-5124.

Chiral Brönsted-acid/base with metal activated substrates Chiral Brönsted acid/base catalyst: a powerful strategy. In combination with transition-metal, 3 approaches:

Chiral Brönsted base and transition-metal Lewis acid Enantioselective aza-Henry reaction, K. R. Knudsen, K. A. Jorgensen, Org. Biomol. Chem. 2005, 3, 1362-1364.

Chiral Brönsted base and transition-metal Lewis acid Enantioselective Conia-ene reaction T. Yang, A. Ferrali, F. Sladojevich, L. Campbell, D. J. Dixon, J. Am. Chem. Soc. 2009, 131, 9140-9141.

Cooperative Reactions: Brönsted acid/base Aminocatalysis Lewis Base Cooperative Reactions: Transition Metal + Organocatalyst NHC organocatalyst Bifunctional catalyst

Organic Lewis base with transition-metal activated electrophiles Krische in 2003, Few examples probably because of compatibility problems B. G. Jellerichs, J.-R. Kong, M. J. Krische J. Am. Chem. Soc. 2003, 125, 7758-7759.

Organic Lewis base catalysed tandem reaction Wu et al. reported a 3 components reaction, S. Ye, J. Wu, Tetrahedron Lett. 2009, 50, 6273-6275.

Cooperative Reactions: Brönsted acid/base Aminocatalysis Lewis Base Cooperative Reactions: Transition Metal + Organocatalyst NHC organocatalyst Bifunctional catalyst

Bifunctional catalyst New generation of catalyst Enhance the compatibility between the metal and the organocatalyst New strategy for cooperative catalysis

Bifunctional organocatalyst in cooperation with transition metal Jun and co-workers, C.-H. Jun, H. Lee, H. Lee, J.-B. Hong, Angew. Chem. Int. Ed. 2000, 39, 3070-3072.

Bifunctional organocatalyst in cooperation with transition metal Wang et al, Maximize the compatibility between the Lewis base and Lewis acid Z. Xu, P. Daka, I. Budik, H. Wang, F. Q. Bai, H.-X. Zhang, Eur. J. Org. Chem. 2009, 4581-4585.

Cooperative Reactions: Brönsted acid/base Aminocatalysis Lewis Base Cooperative Reactions: Transition Metal + Organocatalyst NHC organocatalyst Bifunctional catalyst

NHC-mediated reactions Bode and Glorius in 2004, Tool to develop enantioselective tandem reaction Application in cooperative catalysis, but compatibility? S. Sohn, E. L. Rosen, J. W. Bode, J. Am. Chem. Soc. 2004, 126, 14370-14371. C. Burstein, F. Glorius, Angew. Chem. Int. Ed. 2004, 43, 6205-6208. V. Nair, R. S. Menon, A. T. Biju, C. R. Sinu, R. R. Paul, A. Josea, V. Sreekumarc, Chem. Soc. Rev. 2011, 40, 5336-5346.

NHC-catalysed cooperative reaction Scheidt et al. in 2011, The Lewis acid coordinate and activate the α-ketoester New class of electrophiles for NHC-catalysed annulation D. T. Cohen, B. Cardinal-David, K. A. Scheidt, Angew. Chem. Int. Ed. 2011, 50, 1678-1682

Conclusion Cooperative catalysis between transition metal and organocatalyst attracted much interest: Successfully promoting a variety of transformations Different combinations of metal and organocatalyst Development of new reactions To be continued …