Catalytic asymmetric epoxidation of enones using La-BINOL-triphenylarsine oxide complex: Structural determination of the asymmetric catalyst

T. Nemoto, T. Ohshima, K. Yamaguchi, M. Shibasaki

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Abstract

The catalytic asymmetric epoxidation of enones using the La-BINOL-Ph3As=O complex generated from La(O-i-Pr)3, BINOL, and Ph3As=O in a ratio of 1:1:1 is described herein. Using 1-5 mol % of the asymmetric catalyst, a variety of enones, including a dienone and a cis-enone, were found to be epoxidized in a reasonable reaction time, providing the corresponding epoxy ketones in up to 99% yield and with more than 99% ee. The possible structure of the actual asymmetric catalyst has been clarified by various methods, including X-ray crystal structure analysis. This is the first X-ray analysis of an alkali-metal free lanthanoid-BINOL complex. Although La(binaphthoxide)2(Ph3As=O)2 (7) was observed as the major complex in the complexes' solution, generated from La(O-i-Pr)3, BINOL, and Ph3As=O in a ratio of 1:1:1, the possible active species turned out to be the La-BINOL-Ph3As=O complex in a ratio of 1:1:1. A probable reaction mechanism of the catalytic asymmetric epoxidation of enones is also proposed, suggesting that preferential formation of a heterochiral complex is the reason for asymmetric amplification. Moreover, the interesting role of La(O-i-Pr)3 for accelerating the epoxidations while maintaining high ee's is discussed.

Original languageEnglish
Pages (from-to)2725-2732
Number of pages8
JournalJournal of the American Chemical Society
Volume123
Issue number12
DOIs
Publication statusPublished - Oct 10 2001
Externally publishedYes

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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