Ts instead of Ar F2 If such a reaction could be realized, the enormous pool of commercial enantiopure alcohols and amines (and the wide array of methods to prepare them) which serve as precursors to sulfonylhydrazides could be leveraged. Disclosed herein is the realization of this design thereby enabling the first stereoretentive radical cross-couplings. The reaction is scalable, homogeneous, uses a process-friendly solvent system (t-amyl alcohol), and is hypothesized to proceed via an unprecedented diazine-linked Ni-catalytic cycle as supported by computation (vide infra). Studies commenced using the enantioenriched sulfonylhydrazide 11 (97.5 : 2.5 e.r., Table With an optimized set of conditions established for substrate 11, attention turned to evaluate the generality of enantiospecific sulfonylhydrazide coupling. A focus was placed on 3-arylpiperidine and pyrrolidines given their prevalence in medicinal chemistry (>78,000 known molecules contain these substructures). Pyridine, pyrimidines, pyridazines, pyridones and arenes were evaluated and found to be well-tolerated. Various substituents such as electron-withdrawing groups, electrondonating groups and halogens (chloro and fluoro) on the (hetero)arenes were explored as well.