Concise Synthesis of (-)-GA18 Methyl Ester

J Am Chem Soc. 2023 Jan 11;145(1):53-57. doi: 10.1021/jacs.2c12470. Epub 2022 Dec 27.

Abstract

Gibberellins (GAs) are important plant hormones, but some of their family members are in extremely limited natural supply including GA18. Herein, we report a concise synthesis of (-)-GA18 methyl ester, a member of the C20 gibberellins, from commercially available and cheap andrographolide. Our synthesis features an intramolecular ene reaction to form the C ring, an oxidative cleavage followed by aldol condensation to realize a ring contraction and form the challenging trans-hydrindane (AB ring), and a photochemical [2+2] cycloaddition accompanied by a subsequent SmI2-mediated skeletal rearrangement to construct the methylenebicyclo[3.2.1]octanol moiety (CD ring).

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, N.I.H., Extramural

MeSH terms

  • Cyclization
  • Esters*
  • Gibberellins*
  • Plant Growth Regulators
  • Stereoisomerism

Substances

  • Gibberellins
  • Esters
  • Plant Growth Regulators