A Diosphenol-Based Strategy for the Total Synthesis of (−)-Terpestacin

Barry M. Trost,* Guangbin Dong, and Jennifer A. Vance
Department of Chemistry, Stanford University, Stanford, California 94305-5080
J. Am. Chem. Soc., 2007, 129 (15), pp 4540–4541
DOI: 10.1021/ja070571s
Publication Date (Web): March 8, 2007
Copyright © 2007 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.

, bmtrost@stanford.edu

Abstract

Abstract Image

A novel diosphenol-based strategy has been developed for the enantioselective synthesis of (−)-terpestacin by multiple usage of the α-diketone functionality, first in the “Pd AAA−Claisen rearrangement” protocol, and second by the employment of its oxidized form, the ene-1,2-dione, as an excellent Michael acceptor. This synthesis demonstrates that the sequence of O-allylation−Claisen rearrangement provides a chemo- and regioselective enolate allylation, which can be performed asymmetrically with respect to the enolate or allyl fragment or both. In addition, many interesting chemoselectivity issues, including a highly selective RCM and a dihydroxylation, have been addressed. Overall, this synthesis was accomplished in 20 longest linear steps (24 total steps) from the inexpensive and commercially available 3-methyl-1,2-cyclopentanedione.

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History

  • Published In Issue April 18, 2007
  • Received January 25, 2007

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