Mechanism and Origin of Nickel-Catalyzed Decarbonylative Construction of C(sp²)–C(sp³) Bonds from Carboxylic Acids and Their Derivatives

Nickel-catalyzed arylation of carboxylic acids provides a ligand-controlled chemoselectivity-switchable method for the construction of C(sp²)-C(sp³) bonds. Here, we employed density functional theory to provide a detailed understanding of the mechanism and origin of nickel-catalyzed ligand-controlled carbonyl transformation. This reaction generates decarbonylation products through oxidative addition, activation of C-C bonds, decarbonylation, binding of alkyl radicals with Ni(III) complexes, and final reduction elimination step. The activation of C-C bonds in aromatic carboxylate esters is more favorable than C-O bond activation because of the interaction between the nickel catalyst and the π orbitals of the substrate's aromatic moiety during C-C bond activation. The induction effect of the ligand and the carbonyl group together determines the transfer tendency of the carbonyl group.