Total synthesis of (+)-sarain A

J Am Chem Soc. 2007 Oct 3;129(39):11987-2002. doi: 10.1021/ja074300t. Epub 2007 Sep 12.

Abstract

This article describes the details of our synthetic studies toward the complex marine alkaloid sarain A. Various strategies were conceived, setbacks encountered, and solutions developed, ultimately leading to a successful enantioselective total synthesis. Our route to (+)-sarain A features a number of key steps, including an asymmetric Michael addition to install the C4'-C3'-C7' stereotriad, an enoxysilane-N-sulfonyliminium ion cyclization to set the C3 quaternary carbon stereocenter, and assemble the diazatricycloundecane core, a ring-closing metathesis to construct the 13-membered ring, an intramolecular Stille coupling to fashion the unsaturated 14-membered macrocycle, and a late-stage installation of the tertiary amine-aldehyde proximity interaction.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkaloids / chemical synthesis
  • Alkaloids / chemistry
  • Alkanes / chemical synthesis
  • Animals
  • Bridged-Ring Compounds / chemical synthesis*
  • Bridged-Ring Compounds / chemistry
  • Cyclization
  • Models, Molecular
  • Porifera
  • Stereoisomerism

Substances

  • Alkaloids
  • Alkanes
  • Bridged-Ring Compounds
  • sarain A
  • undecane