title: Asymmetric Activation.
abstract: While nonracemic catalysts can generate nonracemic products with or without the nonlinear relationship in enantiomeric excesses between catalysts and products, racemic catalysts inherently give only a racemic mixture of chiral products. Asymmetric catalysts, either in nonracemic or racemic form, can be further evolved into highly activated catalysts with association of chiral activators. This asymmetric activation process is particularly useful in racemic catalysis through selective activation of one enantiomer of the racemic catalyst. Recently, a strategy whereby a racemic catalyst is selectively deactivated by a chiral additive has been reported to yield nonracemic products. However, reported herein is an alternative and conceptually opposite strategy in which a chiral activator selectively activates, rather than deactivates, one enantiomer of a racemic chiral catalyst. The advantage of this activation strategy over the deactivation counterpart is that the activated catalyst can produce a greater enantiomeric excess in the products-even with the use of a catalytic amount of activator relative to chiral catalyst-than that attained by the enantiomerically pure catalyst on its own. Therefore, asymmetric activation could provide a general and powerful strategy for not only the use of atropisomeric, racemic ligands but also chirally flexible and proatropisomeric ligands without enantiomeric resolution!
authors.affiliation: Department of Chemical Technology Tokyo Institute of Technology Meguro-ku, Tokyo 152-8552 (Japan).
authors.initials: K
authors.lastname: Mikami
authors.initials: M
authors.lastname: Terada
authors.initials: T
authors.lastname: Korenaga
authors.initials: Y
authors.lastname: Matsumoto
authors.initials: M
authors.lastname: Ueki
authors.initials: R
authors.lastname: Angelaud