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Synlett 1995; 1995(2): 173-174
DOI: 10.1055/s-1995-4914
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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
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Publication Date:
31 December 2000 (online)

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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