Direct Catalytic C(sp ² )–SuFEx Coupling of Sulfonyl Fluorides with Unactivated Arenes

Sulfur–fluoride exchange (SuFEx) is a powerful platform for constructing diverse functional molecules, yet catalytic C(sp2)–SuFEx reactions of sulfonyl fluorides remain underexplored. Here, we report a silylium Lewis-acid-catalyzed coupling of sulfonyl fluorides with unactivated arenes. The method tolerates diverse substrates, uses simple arenes, and proceeds under solvent-, transition-metal-, and additive-free conditions with scalable synthesis. Mechanistic studies reveal efficient S–F activation by silylium ion pairs, enabling C–SuFEx sulfone formation.