Recent Advances in Ni‐Catalyzed Asymmetric Dicarbofunctionalization of Alkenes

The asymmetric dicarbofunctionalization of alkenes via nickel catalysis represents a robust platform for the rapid synthesis of enantioenriched compounds from inexpensive and readily obtainable precursors. This approach enables the one‐step addition of two carbon fragments to an alkene, thus providing rapid access to intricate chiral structures that would be difficult to construct using conventional multistep sequences. The unique redox flexibility of nickel, together with its ability to engage radical intermediates and suppress competitive β‐hydride elimination, has enabled diverse enantioselective transformations under reductive, photoredox, and directing‐group‐assisted manifolds. Recent advances have delivered a broad range of asymmetric carboarylation, carboalkenylation, carboacylation, carboalkylation, carbocyanation, and cyclization‐type dicarbofunctionalization reactions. These developments not only expand the synthetic utility of nickel catalysis but also provide valuable opportunities for stereocontrolled C─C bond formation. Recent progress in the nickel‐catalyzed asymmetric dicarbofunctionalization of alkenes, focusing on reaction design, substrate generality, stereochemical control, and mechanistic insights. Current challenges and future opportunities are also discussed, including broader substrate generality, greener reductive systems, electrochemical variants, and more predictive models for enantioselective nickel catalysis.