Synthesis of the bis-spiroacetal moiety of spirolides B and D

Org Lett. 2005 Aug 4;7(16):3497-500. doi: 10.1021/ol051260u.

Abstract

An enantioselective synthesis of the bis-spiroacetal fragment of spirolides B and D is reported. The carbon framework was constructed via Barbier reaction of dihydropyran 3 with aldehyde 4, followed by a double oxidative radical cyclization to construct the bis-spiroacetal. A silyl-modified Prins cyclization and enantioselective crotylation successfully installed the stereocenters in the cyclization precursor. The initial unsaturated bis-spiroacetals 2a-d underwent equilibration during epoxidation to trans-epoxide 14 that was converted to a tertiary alcohol. [reaction: see text]

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetals / chemical synthesis*
  • Acetals / chemistry
  • Animals
  • Cyclization
  • Molecular Structure
  • Mollusca / chemistry
  • Oxidation-Reduction
  • Spiro Compounds / chemical synthesis*
  • Spiro Compounds / chemistry

Substances

  • Acetals
  • Spiro Compounds
  • spirolide B
  • spirolide D