Asymmetric activation

Koichi Mikami, Masahiro Terada, Toshinobu Korenaga, Yousuke Matsumoto, Makoto Ueki, Rémy Angelaud

Research output: Contribution to journalReview articlepeer-review

172 Citations (Scopus)

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!

Original languageEnglish
Pages (from-to)3532-3556
Number of pages25
JournalAngewandte Chemie - International Edition
Volume39
Issue number20
DOIs
Publication statusPublished - 2000 Oct 16
Externally publishedYes

Keywords

  • Asymmetric catalysis
  • Chiral poisoning
  • High-throughput screening
  • Nonlinear effects

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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