Download PDF
Synlett 1995; 1995(2): 173-174
DOI: 10.1055/s-1995-4914
letter
© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or commercialization outside the narrow limits set by copyright legislation, without the publisher's consent, is illegal and liable to criminal prosecution. This applies in particular to photostat reproduction, copying, cyclostyling, mimeographing or duplication of any kind, translating, preparation of microfilms, and electronic data processing and storage.

Conjugate Addition of Alkenylsulfides with α,β-Unsaturated Carbonyl Compounds. Remarkable n-π* Orbital Interaction for Control of Regio- and Stereochemistry

Masaru Takayanagi, Keiji Tanino, Isao Kuwajima*
  • *Department of Chemistry, Tokyo Institute of Technology, Meguro, Tokyo 152, Japan
Further Information

Publication History

Publication Date:
31 December 2000 (online)

  PDF Download  Permissions and Reprints All articles of this category

A highly stereoselective conjugate addition reaction with α,β-unsaturated aldehydes was developed by using alkenylsulfide as a nucleophile. Under the influence of TiCl3(O i Pr), (1S*,2S*)-1-butyl-2-[(1Z)-1-(methylthio)propenyl]-1-(triethylsiloxy)cyclopentane reacted with enals to give 11,12-dimethyl-10-(methylthio)-14-(triethylsiloxy)-9,13-tetradecadien-5-one derivatives in >99% anti selectivity. The high regio- and stereoselection can be explained by assuming the chair-like six-membered cyclic transition state involving the orbital interaction between the sulfur and a carbonyl carbon.

alkenyl sulfide - conjugate addition - enal - enone - stereochemistry

      >