In summary, a straightforward access to α-functionalized β-amino acid motifs via a cooperative Ni/diboron-catalyzed cascade 1,2-N-shift/C-H bond coupling, halogenation, and selenation of α-amino-β-bromo acid esters was reported for the first time. Mechanistically, the N→B coordinated complex generated in-situ appears to be a crucial 1,2-N-shift precursor to weaken the C(sp 3 )-N bond, which enables radical 1,2-amino migration without the aid of a π-system. Interestingly, these results uncovered that the diboron compounds (i.e., B2neo2) functions as not only a reductive agent for Ni(II)→Ni(I) catalytic cycle, but also an activator for the inert C(sp 3 )-N bond in the rearrangement. In addition, this tertiary amino migration converts a nucleophilic alkyl radical into an electrophilic acetonyl radical, which facilitates further radical relay reaction, thereby realizing a new radical cascade merging 1,2-N-shift with C-H coupling, halogenation and selenation. Taken together, the radical relay is catalyzed by a combination of bench-stable Ni/bipyridine-ligand/diboron at ambient temperature and exhibits a broad scope and excellent regioselectivity and diastereoselectivity, which provides a powerful platform for the synthesis of βamino acid motifs via a 1,2-N-migration without the aid and involvement of common π-system for the synthetic community.