Biocatalytic Enantioselective Oxidation of <i>N</i> -Acyl- <i>S</i> -Methyl Sulfenamides for the Asymmetric Synthesis of <i>S</i> -Methyl Sulfoximines

Enantioenriched sulfinamides serve as key intermediates for the asymmetric synthesis of sulfoximines and other S(VI) pharmacophores. Enantioselective biocatalytic oxidation of an <i>S</i>-methyl sulfenamide to the corresponding <i>S</i>-methyl sulfinamide proceeds in good yield and >99:1 er. Its utility as a key chiral intermediate was demonstrated by stereoretentive <i>S</i>-arylation and <i>S</i>-alkylation as well as by the asymmetric synthesis of two <i>S</i>-methyl sulfoximine drug candidates, with <i>S</i>-methyl substitution notably present in most sulfoximine clinical candidates.