Chemodivergent Nickel(0)-Catalyzed Arene C-F Activation with Alkynes: Uriprecedented C-F/C-H Double Insertion

Nickel-catalyzed C-F activations enabled chemodivergent C-C formation with alkynes by chelation assistance. The judicious choice of the alkyne electronic properties allowed the selective synthesis of double-insertion aromatic homologation or alkyne monoannulation products by C-F/C-H activation. On the basis of the unambiguous crystallographic characterization of an unprecedented nine-membered nickelacyclic intermediate and extensive DFT studies, a plausible mechanistic rationale was established for the selective C-F activation and the chemodivergent catalysis.