Enantioselective Synthesis of Sulfilimines Enabled by Photoinduced Copper-Catalyzed C(sp³)-H Sulfimidation

Chiral sulfilimines, as a classic type of organosulfur molecule, are indispensable in synthetic chemistry and pharmaceutical applications, underscoring the significance of their catalytic asymmetric synthesis. While asymmetric S-functionalization of sulfenamides has recently emerged as an effective strategy for accessing chiral sulfilimines, feasible approaches that enable the S-chirality to be created via C(sp³)-H sulfimidation between sulfenamides and hydrocarbons remain exceedingly rare and synthetically challenging. Herein, we describe a photoinduced copper-catalyzed C(sp³)-H sulfimidation, allowing for a straightforward synthesis of highly enantioenriched sulfilimines from simple hydrocarbon feedstocks. Computational studies and mechanistic investigations unveil the outer-sphere S_H2 reaction mechanism of the C-S bond formation step.