Ladder polyether synthesis via epoxide-opening cascades using a disappearing directing group

J Am Chem Soc. 2006 Feb 1;128(4):1056-7. doi: 10.1021/ja057973p.

Abstract

The combination of a trimethylsilyl group, a Brønsted base, a fluoride source, and a hydroxylic solvent enables the first construction of the tetrad of tetrahydropyran rings found in the majority of the ladder polyether natural products by way of a cascade of epoxide-opening events that emulates the final step of Nakanishi's proposed biosynthetic pathway. The trimethylsilyl group disappears during the course of the cascade, and thus these are the first epoxide ring-opening cascades that afford ladder polyether subunits containing no directing groups at the end of the cascade.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Ciguatoxins / chemistry
  • Epoxy Compounds / chemistry*
  • Ethers, Cyclic / chemistry*
  • Furans / chemistry
  • Molecular Conformation
  • Mollusk Venoms
  • Oxocins / chemistry
  • Polycyclic Compounds / chemistry
  • Polymers / chemistry*

Substances

  • Epoxy Compounds
  • Ethers, Cyclic
  • Furans
  • Mollusk Venoms
  • Oxocins
  • Polycyclic Compounds
  • Polymers
  • adriatoxin
  • gambierol
  • gymnocin A
  • gymnocin-B
  • Ciguatoxins
  • gambieric acid A
  • gambieric acid B
  • yessotoxin