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.