Dual ligands relay-promoted transformation of unstrained ketones to polyfluoroarenes and nitriles

C-C bond activation has emerged as a powerful tool for the construction of complex molecules. Herein, we report a dual ligands relay-promoted transformation of unstrained aryl, alkenyl and alkynyl ketones to the corresponding polyfluoroarenes and nitriles via C-C (=O) bond cleavage and subsequent decarboxylative arylation process. Various polyfluoroarene and nitrile products are obtained in one pot under cyanide-free conditions. The protocol features high atom economy, broad functional group tolerance and excellent heterocyclic compatibility. The late-stage functionalization of the drug and natural product demonstrated the synthetic utility of our protocol. Furthermore, the decisive role of the dual ligands was clarified and the mechanistic rationale including the β−C elimination as the rate-limiting step was supported by detailed density functional theory (DFT) studies.