Direct Catalytic Asymmetric Aldol-Tishchenko Reaction

Vijay Gnanadesikan, Yoshihiro Horiuchi, Takashi Ohshima, and Masakatsu Shibasaki*
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Tokyo 113-0033, Japan
J. Am. Chem. Soc., 2004, 126 (25), pp 7782–7783
DOI: 10.1021/ja047906f
Publication Date (Web): June 4, 2004
Copyright © 2004 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, mshibasa@mol.f.u-tokyo.ac.jp

Abstract

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A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

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History

  • Published In Issue June 30, 2004
  • Received April 12, 2004

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