To provide mechanistic insight, experimental and computational studies were performed. A series of radical trapping experiments were carried out to probe the proposed nickel catalyzed radicalradical cross-coupling pathway (vide infra). Benzyl acrylate was selected as an electron deficient alkene for the Giese reaction 27 wherein the 𝛼-amino radical addition product was isolated in 30% yield (Scheme 2A). Swapping the radical scavenger to diphenyl diselenide, which has been used as a trapping agent for acyl radicals, 28 afforded the acyl-selenide product in 15% yield based on GCMS analysis. These experiments indicated that both carbon-centered radicals were involved in the transformation, and the use of TEMPO as an additive completely inhibited the reaction.