Gold(I)-Catalyzed Propargyl Claisen Rearrangement

Benjamin D. Sherry and F. Dean Toste*
Center for New Directions in Organic Synthesis, Department of Chemistry, University of California, Berkeley, California 94720
J. Am. Chem. Soc., 2004, 126 (49), pp 15978–15979
DOI: 10.1021/ja044602k
Publication Date (Web): November 18, 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.

, fdtoste@uclink.berkeley.edu

Abstract

Abstract Image

Homoallenic alcohols are prepared from propargyl vinyl ethers using a trinuclear gold(I)−oxo complex, [(Ph3PAu)3O]BF4, as a catalyst for propargyl Claisen rearrangement at room temperature. The gold(I)-catalyzed reaction is effective for a diverse collection of propargyl vinyl ethers, including substrates containing aryl and alkyl groups at the propargylic position, and hydrogen, aryl, and alkyl substituents at the alkyne terminus. Tertiary propargyl vinyl ethers can be employed in the reaction, at slightly elevated temperatures, to afford tetrasubstituted allenes. Importantly, the rearrangement of 1,2-disubstituted vinyl ethers proceeds with excellent diastereoselectivity, and the rearrangement of chiral nonracemic propargyl vinyl ethers proceeds with excellent chirality transfer to furnish enantioenriched allenes.

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History

  • Published In Issue December 15, 2004
  • Received September 6, 2004

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