Nickel/Light-Driven Catalysis Enables Site-Selective Sulfoximination of Electron-Rich Arenes

Aryl sulfoximines have emerged as privileged motifs in drug discovery, offering a versatile alternative to sulfonamides and sulfones due to their unique physicochemical and pharmacological properties. However, the direct synthesis of N-aryl sulfoximines from electron-rich arenes remains challenging. Here, we present a nickel/light-driven N-arylation of sulfoximines using redox-active arylthianthrenium salts, providing a general and efficient strategy for constructing C–N bonds across a broad range of sulfoximines. The method also exhibits broad applicability to sulfamides and imines, enabling late-stage functionalization of pharmaceutically relevant molecules and direct access to free anilines. Mechanistic investigations, including radical quenching, control experiments, and Hammett analysis, support a nickel/light-induced radical pathway.