A Unified Radical C–SuFEx Platform via Catalytic EDA Complex‐Mediated S(VI)─F Bond Activation

ABSTRACT Sulfur(VI) Fluoride Exchange (SuFEx) chemistry has emerged as a powerful tool for forging diverse molecular architectures. While sulfur(VI) fluorides are typically employed as S(VI) + electrophiles in defluorinative reactions with heteroatom nucleophiles, the direct formation of S(VI)─C bonds via C–SuFEx processes remains a significant challenge and is largely underdeveloped. Herein, we report a general and practical radical‐based C‐SuFEx platform that enables the ligation of sulfonyl and sulfonimidoyl fluorides with alkenes and alkynes, providing direct access to alkynyl sulfones, alkenyl sulfones, and alkenyl sulfonimidoyl derivatives. Mechanistic studies support the involvement of a catalytic electron donor–acceptor (EDA) complex formed between triarylamines and sulfur(VI) fluorides, which facilitates mild activation of S(VI)–F bonds to generate key sulfur(VI)‐centered radicals. The synthetic utility of this methodology is further demonstrated through sequential C–SuFEx/cycloaddition transformations, offering a versatile and modular route to structurally diverse and functionally enriched molecular frameworks.