As important building blocks for bioactive scaffolds, βamino acid motifs exist in many medicinal molecules, such as Taxol, Bestain, and Jasplakinolide (Figure ). Therefore, the continued expansion of highly efficient and selective synthetic technology for novel β-amino acid derivatives is still in high demand by organic and medicinal chemists. With this background in mind, we want to demonstrate the first example merging π-system-independent 1,2-N-shift with C-H coupling, halogenation, or selenation using a Ni/diboron-catalyzed radical relay strategy, which readily leads to valuable β-amino acid derivatives (Scheme 1e). In the presence of a bench-stable NiBr2(dme)/pyridine-imidazoline/B2neo2 catalyst, the nascent α-carboxyl radical formed from the radical 1,2-N shift smoothly undergoes C-H coupling, halogenation, and selenation. This process might represent a new mode of π-system-independen 1,2-N-shift toward β-amino acids. α-Amino-β-bromo acid esters have also been extended as a molecular skeleton for 1,2amino rearrangement. The diboron compound was observed to function as both the activating agent for the cleavage of inert C-N bond and a reductive precursor for Ni(II)→ Ni(I) catalytic cycle. Taken together, these new radical cascades are achieved under mild reaction conditions that avoid the use of oxidants, strong bases, and elevated temperatures. Furthermore, they exhibit broad scope and high diastereoselectivity (> 20:1 dr), and allow for an elusive one-pot synthesis of β-amino acid esters such as ethyl tetrahydroisoquinoline-4-carboxylate. In addition, preliminary density functional theory (DFT) computations uncover a novel Ni/B2neo2-catalyzed 1,2-N-migration process via a reasonable B/N-coordinated intermediate to facilitate the 1,2-N-shift via the inert C(sp 3 )-N cleavage.