Asymmetric total synthesis of (-)-plicatic acid via a highly enantioselective and diastereoselective nucleophilic epoxidation of acyclic trisubstitued olefins

J Am Chem Soc. 2009 Aug 5;131(30):10384-5. doi: 10.1021/ja9039407.

Abstract

The first total synthesis of (-)-plicatic acid has been achieved by a concise and enantioselective route. In this synthesis, a conceptually new strategy featuring an asymmetric epoxidation-intramolecular epoxy-ring-opening Friedel-Crafts reaction sequence was developed for the stereoselective construction of the 2,7'-cyclolignane skeleton bearing contiguous quaternary-quaternary-tertiary stereocenters. The implementation of this strategy was enabled by the development of a modified protocol for the Seebach epoxidation with TADOOH, which affords an unprecedented, highly enantioselective and diastereoselective epoxidation with a range of alpha-carbonyl-beta-substituted acrylates 3.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Alkenes / chemistry*
  • Epoxy Compounds / chemistry*
  • Lignans / chemical synthesis*
  • Lignans / chemistry*
  • Naphthols / chemical synthesis*
  • Naphthols / chemistry*
  • Stereoisomerism
  • Substrate Specificity

Substances

  • Alkenes
  • Epoxy Compounds
  • Lignans
  • Naphthols
  • plicatic acid