Stereoselective alpha,alpha '-Annelation Reactions of 1,3-Dioxan-5-ones

Research output: Contribution to journalArticle

Authors

  • J Carlisle
  • P Tisselli
  • Louise Male
  • Neil Spencer
  • TC Casey

Colleges, School and Institutes

Abstract

Pyrrolidine enamines derived from three 1,3-dioxan-5-ones undergo (alpha,alpha'-annelation reactions with methyl alpha-(bromomethyl)acrylate to produce bridged 2,4-dioxabicyclo[3.3.1]-nonane ring systems with complete stereocontrol. Stereochemical outcomes have been rationalized based on steric and stereoelectronic interactions in intermediate boat-like conformations of the 1,3-dioxane ring and subsequent kinetic protonation to set an axial ester group on the cyclohexanone ring. Base-mediated ester epimerization provides the stereochemical array found in the highly oxygenated cyclohexane ring of phyllaemblic acid and glochicoccins B and D.

Details

Original languageEnglish
Pages (from-to)7461-7464
Number of pages4
JournalThe Journal of Organic Chemistry
Volume75
Issue number21
Publication statusPublished - 1 Nov 2010