Attractive noncovalent interactions in asymmetric catalysis: Links between enzymes and small molecule catalysts
- 18 October 2010
- journal article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences of the United States of America
- Vol. 107 (48), 20678-20685
- https://doi.org/10.1073/pnas.1006402107
Abstract
Catalysis by neutral, organic, small molecules capable of binding and activating substrates solely via noncovalent interactions--particularly H-bonding--has emerged as an important approach in organocatalysis. The mechanisms by which such small molecule catalysts induce high enantioselectivity may be quite different from those used by catalysts that rely on covalent interactions with substrates. Attractive noncovalent interactions are weaker, less distance dependent, less directional, and more affected by entropy than covalent interactions. However, the conformational constraint required for high stereoinduction may be achieved, in principle, if multiple noncovalent attractive interactions are operating in concert. This perspective will outline some recent efforts to elucidate the cooperative mechanisms responsible for stereoinduction in highly enantioselective reactions promoted by noncovalent catalysts.Keywords
This publication has 48 references indexed in Scilit:
- Enantioselective Thiourea-Catalyzed Cationic PolycyclizationsJournal of the American Chemical Society, 2010
- A Medicinal Chemist’s Guide to Molecular InteractionsJournal of Medicinal Chemistry, 2010
- Asymmetric Cooperative Catalysis of Strong Brønsted Acid–Promoted Reactions Using Chiral UreasScience, 2010
- Scaleable catalytic asymmetric Strecker syntheses of unnatural α-amino acidsNature, 2009
- Mechanism of Amido-Thiourea Catalyzed Enantioselective Imine Hydrocyanation: Transition State Stabilization via Multiple Non-Covalent InteractionsJournal of the American Chemical Society, 2009
- Enantioselective Claisen Rearrangements with a Hydrogen-Bond Donor CatalystJournal of the American Chemical Society, 2008
- Enantioselective Thiourea-Catalyzed Additions to Oxocarbenium IonsJournal of the American Chemical Society, 2008
- The Cation−π InteractionChemical Reviews, 1997
- Transition Structure and Substituent Effects on Aqueous Acceleration of the Claisen RearrangementJournal of the American Chemical Society, 1995
- Enzymic Reaction Selectivity by Negative Catalysis or How Do Enzymes Deal with Highly Reactive Intermediates?Angewandte Chemie, 1990