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.