Synthesis of 1,4-Dichloro-1,3-butadienes by Rhodium Complex Catalyzed Reaction of Terminal Alkynes with Trichloroacetyl Chloride

Taigo Kashiwabara, Kouichirou Fuse, Takeshi Muramatsu and Masato Tanaka*
Chemical Resources Laboratory, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
J. Org. Chem., 2009, 74 (24), pp 9433–9439
DOI: 10.1021/jo902088p
Publication Date (Web): November 18, 2009
Copyright © 2009 American Chemical Society

Abstract

Abstract Image

Chlorinative dimerization of terminal alkynes with trichloroacetyl chloride as chlorine donor proceeds in the presence of rhodium catalysts to give (Z,Z)-1,4-dichloro-1,3-butadienes stereoselectively. Ligand screening has revealed that reactions using sterically bulky and electron-donating ligands like trimesitylphosphine are high yielding. The reaction is compatible with a range of functional groups to give the title compounds nearly quantitatively in most cases. A mechanistic possibility involving coupling of β-chloroalken-1-yl intermediate has been discussed.

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History

  • Published In Issue December 18, 2009
  • Article ASAPNovember 18, 2009
  • Received: September 29, 2009

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