Enantioselective S‐Alkylation of Sulfenamides With Copper‐Catalyzed Amino‐Radical‐Transfer Deboronation

This work reports a copper‐catalyzed enantioselective S‐alkylation of sulfenamides enabled by an amino‐radical‐transfer deboronation pathway. Chiral sulfilimines are obtained in high yields (up to 95%) and enantioselectivities (up to 98% ee) under mild conditions. An isomerizable bis(oxazoline) ligand bearing a bridging CH 2 unit is identified as the key factor for both reactivity and stereoselectivity in the copper‐catalyzed radical‐relay coupling with sulfenamides. The method offers a general platform for accessing enantioenriched S(IV) architectures with aliphatic substituents and demonstrates strong potential for applications in medicinal chemistry.