A New Type of Catalytic Tandem 1,4-Addition−Aldol Reaction Which Proceeds through an (Oxa-π-allyl)rhodium Intermediate

Kazuhiro Yoshida, Masamichi Ogasawara, and Tamio Hayashi*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
J. Am. Chem. Soc., 2002, 124 (37), pp 10984–10985
DOI: 10.1021/ja0271025
Publication Date (Web): August 22, 2002
Copyright © 2002 American Chemical Society
*

 To whom correspondence should be addressed. E-mail:  thayashi@ kuchem.kyoto-u.ac.jp.

Abstract

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The reaction of 9-aryl-9-borabicyclo[3.3.1]nonanes (B-Ar-9BBN) with α,β-unsaturated ketones and aldehydes in the presence of 3 mol % [Rh(OMe)(cod)]2 in toluene at 20 °C for 2 h gave high yields of the tandem 1,4-addition−aldol reaction products with high syn selectivity. The reaction proceeds through the catalytic cycle consisting of 1,4-addition of an organorhodium species to an α,β-unsaturated ketone and the aldol addition of the resulting (oxa-π-allyl)rhodium intermediate to an aldehyde.

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History

  • Published In Issue September 18, 2002
  • Received May 30, 2002

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