Density functional theory calculations have been performed to investigate the nickel-catalyzed[3 + 2]cycloaddition of cyclopropenones and α,β-unsaturated ketones.The computations show that the overall catalytic cycle consists of four major steps,including:(1) C-C oxidative addition of the cyclopropenone to afford the four-membered nickelacycle,(2) isomerization,(3) migratory insertion via a 4,1-insertion fashion,and (4) C-C reductive elimination to deliver the[3+2]cycloaddition product.The enantioselectivity is mainly attributed to the π-π interaction between the diphenylcyclopropenone moiety and the phenyl substituent of the oxazoline ring of the ligand.The chemoselectivity of the C =O versus C =C insertion was rationalized in terms of the steric effect.