Highly Selective 1,3-Isomerization of Allylic Alcohols via Rhenium Oxo Catalysis

Christie Morrill and Robert H. Grubbs*
Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125
J. Am. Chem. Soc., 2005, 127 (9), pp 2842–2843
DOI: 10.1021/ja044054a
Publication Date (Web): February 10, 2005
Copyright © 2005 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.

, rhg@caltech.edu

Abstract

Abstract Image

Two reaction strategies are developed to promote the highly selective 1,3-isomerization of a variety of allylic alcohols using O3ReOSiPh3 as a catalyst. The first strategy utilizes substrates whose 1,3-regioisomer contains a conjugated alkene, which relies on thermodynamics to obtain high selectivity. The second strategy employs N,O-bis(trimethylsilyl)acetamide as an additive to selectively and irreversibly remove the product from the reaction equilibrium and works well for the isomerization of tertiary allylic alcohols into primary allylic alcohols containing trisubstituted alkene components. High stereoselectivity is also observed in the 1,3-isomerization of enantioenriched allylic alcohols.

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History

  • Published In Issue March 09, 2005
  • Received September 29, 2004

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