Nucleophilic epoxidation of gamma-hydroxyvinyl sulfoxide derivatives

J Org Chem. 2003 Jun 13;68(12):4797-805. doi: 10.1021/jo0342828.

Abstract

The nucleophilic epoxidation of simple (gamma-silyloxy)vinyl sulfoxides takes place with complete stereocontrol and high yields. For substrates bearing an additional substituent at the gamma position, a reinforcing/nonreinforcing scenario is operative. While E and Z silylated substrates undergo a primarily sulfur directed epoxidation with good to excellent diastereocontrol, the related (E)-(2-methoxyethoxy)methyl ethers display diminished selectivity for the diastereomer derived from the nonreinforcing scenario.