Tuning of α-Silyl Carbocation Reactivity into Enone Transposition: Application to the Synthesis of Peribysin D, E-Volkendousin, and E-Guggulsterone

Org Lett. 2021 Sep 3;23(17):6642-6647. doi: 10.1021/acs.orglett.1c02173. Epub 2021 Aug 13.

Abstract

A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and Z-selectivity are the highlights of the method. The developed method was applied for the first total synthesis of peribysin D along with its structural revision. Formal synthesis of E-guggulsterone and E-volkendousin was also claimed using a short sequence.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Furans / chemical synthesis*
  • Furans / chemistry
  • Molecular Structure
  • Pregnanes / chemical synthesis*
  • Pregnanes / chemistry
  • Pregnenediones / chemical synthesis*
  • Pregnenediones / chemistry
  • Stereoisomerism

Substances

  • Furans
  • Pregnanes
  • Pregnenediones
  • peribysin D
  • volkendusin diacetate
  • pregna-4,17-diene-3,16-dione