Cycloisomerization of Activated (2E,4Z)-Heptatrienoate and Its Relevance to Crispatene (Bio)synthesis. A Case of Concerted and Stepwise Uncertainty

Carlos Silva López, Olalla Nieto Faza, Rosana Álvarez, and Ángel R. de Lera*
Departamento de Qumica Orgnica, Facultade de Qumica, Universidade de Vigo, Lagoas Marcosende, E-36310, Vigo, Galicia, Spain
J. Org. Chem., 2006, 71 (12), pp 4497–4501
DOI: 10.1021/jo0603274
Publication Date (Web): May 11, 2006
Copyright © 2006 American Chemical Society
*

 Corresponding author:  Fax:  34986811940.

, qolera@uvigo.es

Abstract

Abstract Image

A single transition structure was located on the potential energy surface of the cycloisomerization of protic and Lewis acid activated (2E,4Z)-heptatrienal and the corresponding methyl ester to provide the bicyclo[3.1.0]hexene derivatives, the central skeleton of the crispatene natural products. A two-dimensional scan of the C−C bond-forming reactions revealed a barrierless cyclopropane closure following the pentadienyl cycloisomerization, with preservation of the stereochemical information.

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History

  • Published In Issue June 09, 2006
  • Received February 16, 2006

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