Domino Reaction: First Report
Angew. Chem. 1937, 50, 779–787
Organo-metal
cooperative catalysis
2
Transition metal catalysis
One of the most useful and powerful tool in organic chemistry.
Examples of transition metal reactions: Advantages:
- Cross-coupling - Chemoselectivity
- Hydroformylation - Regioselectivity
- Alkene and alkyne metathesis - Stereoselectivity
- Hydrogenation - High yield
- Cyclopropanation - Reproducibility
- Hydroamination - Low catalyst loading
- Hydroesterification
- Hydrocarboxylation
- Pauson-Khand reaction
- Isomerisation of olefins
- Hydrocyanation
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. 3
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. 4
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. 5
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. 8
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. 9
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. 10
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. 11
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. 12
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. 13
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. 14
Enamine induced enantioselective cooperative reaction
Nishibayashi et al in 2010,
M. Ikeda, Y. Miyake, Y. Nishibayashi, Angew. Chem. Int. Ed. 2010, 49, 7289-7293. 15
