Enantioconvergent Access to Chiral S(VI) Stereocenters by Kinetic Resolution of Sulfonimidoyl Chlorides

Sulfur chirality has recently gained in importance across a wide range of chemical domains. However, the dearth of catalytic approaches for sulfur(VI) stereocenters continues to present a challenge for the broader utilization of chiral-at-sulfur motifs. We report herein the development of a previously unexplored approach for the kinetic resolution of chiral sulfur(VI) functionalities that leverages the electrophilic reactivity of sulfur(VI) stereocenters. This catalytic strategy provides enantioconvergent access to sulfonimidoyl chlorides and sulfonimidates, which are some of the least explored and catalytically accessible stereogenic S(VI) functionalities. This study also elucidates the key roles of noncovalent interactions and highlights the importance of the unfunctionalized backbone of the catalyst in imparting high enantioselectivity to the kinetic resolution of heteroatom stereocenters.