Chemodivergent Nickel(0)-Catalyzed Arene C–F Activation with Alkynes: Unprecedented 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.