Mechanistic Insights into Enantioselective C(sp3)−H Acylation to Construct α‐Amino Ketones via Photoredox and Ni(II) Dual Catalysis: A DFT Study

Abstract The development of the merger of a Ni(II) catalyst with an appropriate photocatalyst under visible‐light irradiation provides a new strategy for realizing direct functionalization of C(sp 3 )−H bonds. Mechanistically, whether the reduction of Ni catalyst to form a Ni(0) species is necessary in the dual catalysis still remains under debate. Herein, DFT calculations were carried out to gain a mechanistic insight into the enantioselective acylation of α‐amino C(sp 3 )−H bonds to furnish α‐amino ketones via photoredox and Ni dual catalysis. A feasible mechanistic pathway for the Ni catalysis via the Ni(I)−Ni(III)−Ni(II)−Ni(III)−Ni(I) cycle is suggested with the sequential elementary steps of oxidative addition, single electron reduction, radical addition, and reductive elimination in leading to the final product, whereas a nickel catalytic cycle, Ni(I)−Ni(0)−Ni(II)−Ni(III)−Ni(I), might not be feasible for the photoredox and Ni dual‐catalyzed acylation of α‐amino C(sp 3 )−H bonds. The origin of the stereoselectivity for this reaction is also discussed, which could be attributed to the minimization of the steric hindrance between the alkyl moiety of radical part and phenyl group of the chiral ligand.