Mechanism of the Gold(I)-Catalyzed Rautenstrauch Rearrangement:  A Center-to-Helix-to-Center Chirality Transfer

Olalla Nieto Faza, Carlos Silva López, Rosana Álvarez, and Angel R. de Lera*
Contribution from the Departamento de Qumica Orgnica, Universidade de Vigo, Lagoas Marcosende, 36310, Vigo, Spain
J. Am. Chem. Soc., 2006, 128 (7), pp 2434–2437
DOI: 10.1021/ja057127e
Publication Date (Web): February 1, 2006
Copyright © 2006 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.

, qolera@uvigo.es

Abstract

Abstract Image

The mechanism of the stereospecific gold(I)-catalyzed Rautenstrauch rearrangement of (E)-1-ethynyl-2-methyl-but-2-en-yl acetate to 3,4-dimethyl-cyclopent-2-enone has been computationally addressed using DFT (B3LYP/6-31G*, SDD for Au). Our results indicate that the bond formation event follows the Au(I)-induced acetyl transfer to the vicinal alkyne and that it is the helicity of the pentadienyl cation intermediate which keeps memory of the chiral information. The fidelity of the center-to-helix-to-center chirality transfer requires that the rates of helix interconversion and pivaloyl rotation are slower than the cyclization, as calculations predict.

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History

  • Published In Issue February 22, 2006
  • Received October 19, 2005

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