title: Electrochemically mediated enantioselective reduction of chiral sulfoxides.
abstract: The respiratory DMSO reductase from Rhodobacter capsulatus catalyzes the reduction of dimethyl sulfoxide to dimethyl sulfide. Herein, we have utilized this Mo enzyme as an enantioselective catalyst to generate optically pure sulfoxides (methyl p-tolyl sulfoxide, methyl phenyl sulfoxide and phenyl vinyl sulfoxide) from racemic starting materials. A hexaaminecobalt coordination compound in its divalent oxidation state was employed as the mediator of electron transfer between the working electrode and DMSO reductase to continually reactivate the enzyme after turnover. In all cases, chiral HPLC analysis of the reaction mixture revealed that the S-sulfoxide was reduced more rapidly leading to enrichment or isolation of the R isomer.
authors.affiliation: School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, 4072, Australia.
authors.forename: Kuan-I
authors.initials: KI
authors.lastname: Chen
authors.forename: Victoria L
authors.initials: VL
authors.lastname: Challinor
authors.forename: Linda
authors.initials: L
authors.lastname: Kielmann
authors.forename: Philip C
authors.initials: PC
authors.lastname: Sharpe
authors.forename: James J
authors.initials: JJ
authors.lastname: De Voss
authors.forename: Ulrike
authors.initials: U
authors.lastname: Kappler
authors.forename: Alastair G
authors.initials: AG
authors.lastname: McEwan
authors.forename: Paul V
authors.initials: PV
authors.lastname: Bernhardt
mesh_terms: D002384:Catalysis; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D008982:Molybdenum / Q000737:chemistry*; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry*; D016354:Rhodobacter capsulatus / Q000201:enzymology*; D013440:Sulfides / Q000737:chemistry; D013454:Sulfoxides / Q000737:chemistry*
chemical_list: D007506:Iron-Sulfur Proteins; D013440:Sulfides; D013454:Sulfoxides; C417240:methyl phenyl sulfoxide; D008982:Molybdenum; D010088:Oxidoreductases; C045664:dimethyl sulfoxide reductase; C004784:dimethyl sulfide; D004121:Dimethyl Sulfoxide