Palladium‐Catalyzed Chemoselective Direct Arylation of Polyfluoroarenes With Chloroaryl Triflates at the C–Cl Bond

ABSTRACT This study describes a palladium‐catalyzed chemoselective direct arylation of polyfluoroarenes with chloro(hetero)aryl triflates, achieving site‐selective functionalization at the C–Cl bond for the first time. The recently developed alkyl‐pyrazole‐based phosphine ligand ( BirdPhos ) proved essential for the success of this transformation, affording excellent yields with high chemoselectivity. Moreover, the catalytic system enables the efficient synthesis of a broad range of functionalized polyfluoroarene derivatives under mild, additive‐free conditions. Notably, the reaction retains the triflate group in the products, providing a versatile functional handle for further derivatization and highlighting the broad applicability and synthetic utility of this method.