Asymmetric total synthesis of Apocynaceae hydrocarbazole alkaloids (+)-deethylibophyllidine and (+)-limaspermidine

J Am Chem Soc. 2015 Apr 1;137(12):4267-73. doi: 10.1021/jacs.5b01926. Epub 2015 Mar 24.

Abstract

An unprecedented asymmetric catalytic tandem aminolysis/aza-Michael addition reaction of spirocyclic para-dienoneimides has been designed and developed through organocatalytic enantioselective desymmetrization. A unified strategy based on this key tandem methodology has been divergently explored for the asymmetric total synthesis of two natural Apocynaceae alkaloids, (+)-deethylibophyllidine and (+)-limaspermidine. The present studies not only enrich the tandem reaction design concerning the asymmetric catalytic assembly of a chiral all-carbon quaternary stereocenter contained in the densely functionalized hydrocarbazole synthons but also manifest the potential for the application of the asymmetric catalysis based on the para-dienone chemistry in asymmetric synthesis of natural products.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Apocynaceae / chemistry*
  • Biological Products / chemical synthesis*
  • Biological Products / chemistry
  • Carbazoles / chemical synthesis
  • Carbazoles / chemistry
  • Catalysis
  • Indole Alkaloids / chemical synthesis*
  • Indole Alkaloids / chemistry
  • Models, Molecular
  • Stereoisomerism

Substances

  • Biological Products
  • Carbazoles
  • Indole Alkaloids
  • limaspermidine