Get access

Synthesis of ent-Kaurane and Beyerane Diterpenoids by Controlled Fragmentations of Overbred Intermediates

Authors

  • Emily C. Cherney,

    1. Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
    Search for more papers by this author
    • These authors contributed equally to this work.

  • Dr. Jason C. Green,

    1. Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
    Search for more papers by this author
    • These authors contributed equally to this work.

  • Prof. Dr. Phil S. Baran

    Corresponding author
    1. Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
    • Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)===

    Search for more papers by this author

  • Financial support for this work was provided by an unrestricted grant from TEVA, the NIH (GM097444-03), and NSF (a predoctoral fellowship to E.C.C). We are grateful to Prof. A. Rheingold and Dr. C. E. Moore (UCSD) for X-ray crystallographic analysis.

Abstract

original image

Efficient access to minimally oxidized members of the ent-kaurane and beyerane class of terpenes has been achieved by using a polyene cyclization precursor designed to directly yield oxidation at the axial C19-methyl group. Construction of the [3.2.1]bicyclic system found in the ent-kaurane skeleton was realized with two overbred intermediates. Wagner–Meerwein rearrangement of the [3.2.1]bicyclic system yields the beyerane skeleton of isosteviol.

Ancillary