Copper-Catalyzed Regio- and Stereo-Defined Protocols to Access β-Aminated Carbonyl Derivatives

We report herein a Cu(I)-catalyzed highly regio- and stereoselective vinylic C-H amination reaction to generate (<i>Z</i>)-enamines, or β-aminated heterocyclic amines and ketones. This strategy involves the Cu^I-Cu^II-Cu^III catalytic cycle-mediated radical addition of <i>in situ</i>-generated N-centered radicals, followed by a stereocontrolled anticoplanar β-H elimination protocol. The β-C-H bond cleavage step is suggested to be involved in the rate-determining step based on the D-labeled kinetic studies.