Total synthesis of (+)-ambruticin S: probing the pharmacophoric subunit

J Org Chem. 2010 Aug 20;75(16):5601-18. doi: 10.1021/jo100956v.

Abstract

An enantioselective synthesis of the antifungal natural product (+)-ambruticin S has been accomplished starting with the readily available methyl alpha-d-glucopyranoside, (R)-Roche ester, and (S)-glycidol as chirons, which encompassed seven of the 10 stereogenic centers of the target molecule. The remaining three centers were set by a highly diastereoselective, asymmetric cyclopropanation employing a chiral, nonracemic phosphonamide reagent. Our strategy for the construction of the dihydropyran subunit involved a highly syn-selective Lewis acid catalyzed 6-endo-trig cyclization. Other key steps in the synthesis featured an epoxide opening with a dithiane anion, two efficient phosphonamide-anion based olefinations, and a late-stage C-glycosylation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Antifungal Agents / chemical synthesis*
  • Antifungal Agents / chemistry
  • Biological Factors / chemical synthesis
  • Biological Factors / chemistry
  • Cyclization
  • Glycosylation
  • Molecular Conformation
  • Pyrans / chemical synthesis
  • Pyrans / chemistry
  • Stereoisomerism

Substances

  • Antifungal Agents
  • Biological Factors
  • Pyrans
  • ambruticin S
  • ambruticin