Understanding the Reaction Mechanism of Nickel-Catalyzed Enantioselective Arylative Activation of the Aromatic C–O Bond

Mild synthetic methods to transform aromatic carbon–oxygen (C–O) bonds into useful molecules have great potential in renewable biomass conversion. Recently, a Ni–NHC (N-heterocyclic carbene) complex catalyzing an asymmetric ring-opening reaction of dinaphthofuran with PhMgCl at room temperature was reported. In this work, we carried out density functional theory (DFT) calculations to investigate the detailed mechanism. The DFT results reveal a novel mechanism that involves Mg(II)–O coordination followed by migration of the phenyl nucleophile to the Ni(0) metal center prior to oxidative addition of a C–O bond to Ni(0). Insights into how the chiral NHC ligand helps induce the enantioselectivity have been obtained.