Regio- and Enantioselective Intermolecular Carbo-halogenation of Alkenes via Nickel/N-Heterocyclic Carbene Catalysis

The intermolecular carbo-halogenation of alkenes provides a direct method for synthesizing alkyl halides. However, existing methods are largely limited to monosubstituted alkenes, and a general catalytic asymmetric intermolecular variant remains an unsolved challenge. Herein, we report a highly regio- and enantioselective intermolecular carbo-halogenation of 1,1-disubstituted alkenes through a nickel/N-heterocyclic carbene (NHC)-catalyzed carbo-magnesiation/electrophilic halogenation strategy. The use of bulky NHC ligands and haloacetonitriles as halogen sources proved crucial for achieving high reactivity and selectivity, facilitating the efficient synthesis of diverse alkyl halides that feature acyclic or cyclic β-all-carbon quaternary centers. This work significantly advances the field of catalytic asymmetric carbo-halogenation.