The physical organic chemistry of free radicals has been widely studied and it is well known that instantaneous racemization occurs upon generation from enantiopure precursors (Figure ). The rate of this process has been measured to be in the picosecond range which is on the time scale of molecular rotations. As such, retaining the chirality of radicals has only been observed in special settings. This basic property of alkyl radicals has rendered their stereoretentive capture with transition metals an elusive goal that is generally regarded as impossible. This has been experimentally verified in multiple contexts such as the reductive crosscoupling of enantiopure alkyl bromides such as 3, the decarboxylative Negishi coupling of 1, or the diastereocontrolled coupling of redox-active ester 6. As such, it is generally assumed that the only conceivable way to achieve enantiocontrolled radical cross-coupling is through radical capture onto a metal center adorned with chiral ligands. Enantioconvergent couplings of this type have been reported, requiring specially designed and optimized ligands for each individual reaction and substrate type. In addition, radical cross-couplings utilizing this strategy often requires stabilized radical donors (benzylic, adjacent to a heteroatom or electron-withdrawing group). This stands in stark contrast to widely employed asymmetric hydrogenation chemistry wherein a relatively small set of chiral ligands can be used to enantioselectively reduce almost every type of olefin. Unlike olefins, which are inherently less structurally diverse, alkyl radical structures encompass much broader 3D chemical space, rendering the identification of general ligand classes that can reliably impart stereocontrol an intractable problem. Further complicating this puzzle from a practical standpoint is the ever-present need for redox chemistry to activate radical precursors. Recently, we disclosed sulfonylhydrazides as redox-neutral radical precursors for cross-coupling that benefit from simple, "Suzuki-like" reaction conditions: an inexpensive Ni-catalyst, mild base, gentle heat, rapid setup, no pyrophoric reagents (alkyl zinc/magnesium), and no external redox additives/catalytic systems (Figure ). Sulfonylhydrazides are uniquely useful radical precursors as they serve as electron donors to activate Ni, and are easily accessible from carbonyl