Base-Mediated Transformation of Glycals to Their Corresponding Vinyl Iodides and Their Application in the Synthesis of C-3 Enofuranose and Bicyclic 3,4-Pyran-Fused Furanose.

Abstract

A simple method for the iodination of unsaturated sugars to form sugar vinyl iodides was developed under oxidant-free conditions using NaH/DMF/iodine as a reagent system at ambient temperature. 2-Iodoglycals bearing ester, ether, silicon, and acetonide protection were synthesized in good to excellent yield. 3-Vinyl iodides derived from 1,2:5,6-diacetonide glucofuranose were transformed to C-3 enofuranose and bicyclic 3,4-pyran-fused furanose via Pd-catalyzed C-3 carbonylation and intramolecular Heck reaction, respectively, as the key step.