Synfacts 2007(3): 0291-0291  
DOI: 10.1055/s-2007-968246
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Desymmetrization: Group-Selective Diels-Alder Reaction

Contributor(s): Hisashi Yamamoto, Matthew B. Boxer
N. Azzi, E. Griffen, M. Light, B. Linclau*
University of Southampton and AstraZeneca, Alderley Park, Macclesfield, UK
Further Information

Publication History

Publication Date:
20 February 2007 (online)

Significance

This paper describes the synthesis of the trans-hydrindene ring, which is a common motif in steroids and subsequently many biologically important molecules. The synthesis of the Diels-Alder precursor requires the synthesis of a skipped diene containing a tertiary carbon in the skipped position. This synthesis was nicely accomplished through protonation of a lithium enolate with acetic acid, generating an unconjugated dienyl ester, which was converted into the aldehyde and subjected to Wittig-Horner olefination. The use of the Evans Cu-bis(oxazoline) catalyst generated the product in 56% yield and 82:18 dr, giving the major isomer in 90% ee.