Nickel-Catalyzed Enantioconvergent SN2 O-Alkylation through Halide-Enabled Dynamic Kinetic Resolution

Metal-catalyzed enantioselective construction of C(sp3)–O bonds from racemic alkyl electrophiles has attracted considerable attention, yet existing approaches typically proceed through organometallic or radical intermediates. Here, we highlight a halide-enabled dynamic kinetic resolution platform that integrates rapid substrate racemization with nickel-catalyzed enantioselective O-alkylation. Bromide ions generated in situ continuously promote reversible SN2 exchange between substrate enantiomers, providing a self-sustained racemization process without external racemization catalysts or additional energy input. Combined with ligand-controlled outer-sphere SN2 substitution, this strategy affords a broad range of enantioenriched hydroxamates in high yields and excellent enantioselectivities under mild, air- and moisture-tolerant conditions. Mechanistic studies support a halide-driven dynamic kinetic resolution coupled with an outer-sphere Ni(II)-mediated substitution pathway, providing a general strategy for asymmetric C(sp3)–O bond formation.