Total Synthesis of (-)-14-Hydroxygelsenicine and Six Biogenetically Related Gelsemium Alkaloids

Org Lett. 2019 Sep 6;21(17):7134-7137. doi: 10.1021/acs.orglett.9b02703. Epub 2019 Aug 12.

Abstract

The first concise and collective asymmetric total synthesis of six 14-hydroxygelsenicine-related Gelsemium alkaloids, i.e., 14-hydroxygelsedilam, 14-acetoxygelsedilam, gelsefuranidine, gelsemolenine A, and gelselegandines B and C, was accomplished via the facile construction of a 7-azabicyclo[4.2.1]nonane skeleton by intramolecular aza-Michael addition, the preparation of an oxabicyclo[3.2.2]nonane ring core with a secondary hydroxy group at C14 by an intramolecular oxymercuration-hydroxylation strategy, and divergent transformations of 14-hydroxygelsenicine into biogenetically related alkaloids.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkaloids / chemical synthesis*
  • Alkaloids / chemistry*
  • Furans / chemical synthesis*
  • Furans / chemistry
  • Gelsemium / chemistry*
  • Indole Alkaloids / chemical synthesis*
  • Indole Alkaloids / chemistry
  • Molecular Conformation
  • Stereoisomerism

Substances

  • (-)-14-hydroxygelsenicine
  • Alkaloids
  • Furans
  • Indole Alkaloids
  • gelsefuranidine