Enantioselective Synthesis of Sulfilimines Enabled by Photoinduced Copper-Catalyzed C(sp ³ )-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(sp 3 )-H sulfimidation between sulfenamides and hydrocarbons remain exceedingly rare and synthetically challenging. Herein, we describe a photoinduced copper-catalyzed C(sp 3 )-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 H 2 reaction mechanism of the C–S bond formation step.