Enantioselective Divergent Syntheses of Diterpenoid Pyrones

J Am Chem Soc. 2024 Apr 3;146(13):9395-9403. doi: 10.1021/jacs.4c01788. Epub 2024 Mar 18.

Abstract

Capitalizing a synergy between late-stage C(sp3)-H alkynylation and a series of transition metal-catalyzed alkyne functionalization reactions, we reported herein enantioselective divergent synthesis of 10 diterpenoid pyrones within 14-16 steps starting from chiral pool enoxolone, including the first enantioselective synthesis of higginsianins A, B, D, E, and metarhizin C. Our synthesis also highlights an unprecedented biomimetic oxidative rearrangement of α-pyrone into 3(2H)-furanone, as well as applications of Echavarren C(sp3)-H alkynylation reaction and Toste chiral counterion-mediated Au-catalyzed intramolecular allene hydroalkoxylation in natural product synthesis.

MeSH terms

  • Biological Products*
  • Pyrones*
  • Stereoisomerism

Substances

  • Pyrones
  • Biological Products