Chloroperoxidase-Catalyzed Asymmetric Synthesis: Enantioselective Reactions of Chiral Hydroperoxides with Sulfides and Bromohydration of Glycals

Article abstract of DOI:10.1021/jo00052a048

This paper describes the use of chloroperoxidase (CPO) from Caldariomyces fumago in the oxidation of sulfides to prepare (R)-sulfoxides with excellent ee (97-100percent) and yield (66-92percent) using H2O2 as oxidant.When racemic 1-phenylethyl hydroperoxides were used in the oxidation of sulfides, the corresponding (R)-alcohol generated from the oxidant and the unreacted (S)-hydroperoxide were recovered with high enantiomeric purity.The enantioselectivity in the enzymatic asymmetric oxidation was found to depend on the concentration of the substrate and enzyme.Chloroperoxidase was also used in the regioselective bromohydration of certain saccharide glycals with KBr and H2O2 to give the corresponding 2-deoxy-2-bromo saccharides.