Catalytic asymmetric oxidative sulfenylation of β-ketocarbonyls using a chiral primary amine

Enantioselective oxidative construction of a C(sp 3 )–S bond has been achieved using a chiral primary amine catalyst in the presence of tert -butyl hydroperoxide and a catalytic amount of tetrabutylammonium iodide. The distinctive feature of the current reaction is coupling with nucleophilic sulfur reactants under oxidative conditions. This protocol provides facile access to chiral thioethers bearing S-containing quaternary stereocenters with good chemo- and enantiocontrol.