DFT insights into the Ni-catalyzed regioselective hydrocarboxylation of unsaturated alkenes with CO.

The nickel-catalyzed hydrocarboxylation of alkenes using carbon dioxide has recently become an appealing method to prepare functionalized carboxylic acids with high efficiency and regioselectivity. Herein, density functional theory (DFT) calculations were conducted on the Ni-catalyzed hydrocarboxylation of aryl-/alkyl-substituted alkenes with CO. The α- and β-carboxylation of aromatic and aliphatic olefins originate from distinct catalytic cycles: H-transfer-carboxylation and carboxylation-H-transfer pathways. The typical hydrometallation-carboxylation mechanism is unlikely because water/carbonic acid (H-resource) are inferior hydride donors.