Differential use of anhydropyranosides for enantiopure routes to bis-gamma-butyrolactones: a new approach to the frameworks of antibiotic and anticancer agents isoavenaciolide and ethisolide

Abstract

Regio- and chemoselective syntheses of enantiopure bis-furanoids are described. These compounds are chirons for several families of bioactive natural products, including isoavenaciolide and ethisolide. Reaction of a 3,4-epoxy pyran with beta-ketoester dianions delivers substituted pyranosides in high yield. Cyclization then yields fused furan-pyran intermediates. Oxidation, deprotection, and rearrangement lead to bis-furanoids that bear the essential framework and stereochemistry of ethisolide and isoavenaciolide.