Unified synthesis of eudesmanolides, combining biomimetic strategies with homogeneous catalysis and free-radical chemistry

Org Lett. 2003 May 29;5(11):1935-8. doi: 10.1021/ol034510k.

Abstract

[reaction: see text] A general procedure for the synthesis of both 12,6- and 12,8-eudesmanolides has been developed. The key step is the titanocene-catalyzed radical cyclization of accessible epoxygermacrolides. The novel reagent 2,4,6-trimethyl-1-trimethylsilylpyridinium chloride, both compatible with oxiranes and capable of regenerating Cp(2)TiCl(2) from Cp(2)Ti(Cl)H and Cp(2)Ti(Cl)OAc, played an important role in the catalytic cycle leading to exocyclic alkenes.

MeSH terms

  • Biomimetics
  • Catalysis
  • Electron Transport
  • Free Radicals / chemistry
  • Indicators and Reagents
  • Magnetic Resonance Spectroscopy
  • Sesquiterpenes / chemistry*

Substances

  • Free Radicals
  • Indicators and Reagents
  • Sesquiterpenes
  • eudesmanolide