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 CH₂ 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.