Enantioselective Synthesis of Chiral γ‐Amino Acid Esters via Photoredox/Nickel‐Catalyzed Aryl‐Aminoalkylation of Alkenes

Comprehensive Summary Chiral γ ‐amino acids are among the most valuable and ubiquitous structural units in natural products, pharmaceuticals and many physiologically active compounds. Herein, we demonstrate a convenient synthetic approach to chiral γ ‐amino acid structures via an asymmetric aryl‐aminoalkylation of alkenes enabled by a dual photoredox/nickel catalysis. Taking advantage of the mild and redox‐neutral condition, high levels of enantiocontrol of α ‐carbonyl benzylic stereocenters are obtained. Experimental and computational mechanistic studies were performed to gain insights into the mechanism and origin of enantioselectivity. The results reveal that the reaction follows a Ni(0)/Ni(I)/Ni(III)/Ni(I) catalytic cycle and C–X bond oxidative addition is the enantiodetermining step.