Asymmetric proton catalysis

Jeff D. McCilvra, Vijaya Bhasker Condi, and Viresh H. Raival 

A-H B interaction Mostly covalent Mostly electrostatic Electrostatic 

Given the infinite variations in bonding patterns, hydrogen bonding is best considered as a continuum of bonding interactions, from weak to strong. Moving 

The systematic use of hydrogen bonding for the promotion of racemic organic reactions began most noticeably during the 1980s, and these studies are summa- 

Over the past half-dozen years, many laboratories have focused their efforts on the development of chiral hydrogen bond donors that function as catalysts for enantioselective organic reactions. One of the earliest successes in this area came from Jacobsen and co-workers, who reported the use of peptide-like chiral urea-based catalysts for the hydrocyanation of aldimines and ketoimines [40, 41]. Several other laboratories have also reported highly enantioselective transformations catalyzed by a chiral hydrogen bond donor. The following sections provide a summary of the many developments in hydrogen bond-catalyzed enantioselective reactions, along with a discussion of mechanisms and selectivity models. 

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Asymmetric Proton Catalysis Table 6.40 Chiral amidinium-catalyzed DA reactions of diketones. 

McGilvra, J.D., Gondi, V.B., and Rawal, V.H. (2007) Asymmetric proton catalysis, in Enantioselective Organocatalysis (ed. P.I. Dalko), Wiley-VCH Verlag GmbH, Weinheim, pp. 189-254. 

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