Anionic Stereogenic-at-Cobalt(III) Complex-Enabled Asymmetric Oxidation of N,N-Dialkyl Sulfenamides

An asymmetric oxidation of N,N-dialkyl sulfenamides is exhibited by using anionic stereogenic-at-cobalt(III) complexes as catalysts. This protocol provides an alternative approach to access a diverse set of chiral tertiary sulfinamides with high enantioselectivities (24 examples, up to 94:6 e.r.). Additionally, control experiments suggest that this protocol could be accomplished through a chiral cationic S(IV) intermediate.