Nonlinear Effects in Asymmetric Synthesis and Stereoselective Reactions: Ten Years of Investigation

Christian Girard; Henri B Kagan

doi:10.1002/(SICI)1521-3773(19981116)37:21<2922::AID-ANIE2922>3.0.CO;2-1

Nonlinear Effects in Asymmetric Synthesis and Stereoselective Reactions: Ten Years of Investigation

Angew Chem Int Ed Engl. 1998 Nov 16;37(21):2922-2959. doi: 10.1002/(SICI)1521-3773(19981116)37:21<2922::AID-ANIE2922>3.0.CO;2-1.

Authors

Christian Girard¹, Henri B Kagan²

Affiliations

¹ Laboratoire de Vectorisation Moléculaire et Cellulaire, Ecole Nationale Supérieure de Chimie de Paris, 11, rue Pierre et Marie Curie, F-75231 Paris Cedex (France).
² Laboratoire des Réactions Organiques Sélectives, Institut de Chimie Moléculaire d'Orsay, Bâtiment 420, Université de Paris-Sud, F-91405 Orsay Cedex (France), Fax: (+33) 169-15-46-80.

Abstract

Who would have thought before 1986 that an enantiomerically impure catalyst could give a product in an asymmetric synthesis with an enantiomeric excess higher than that of the catalyst? Until then it was assumed that the ee value of the product (ee_prod ) from an asymmetric synthesis was linearly correlated to the ee value of the chiral auxiliary (ee_aux )-in fact a large deviation is possible (see diagram). These nonlinear effects are not only of academic interest since they have a variety of practical uses, which are highlighted in this review.

Keywords: Asymmetric amplification; Asymmetric catalysis; Asymmetric synthesis; Autocatalysis; Chiral auxiliaries.

Publication types

Review