Nickel-Catalyzed Remote Substitution of Alcohols

Here, we report a nickel-catalyzed remote substitution of unprotected alkenyl alcohols with arylboronic acids, enabling C-C bond formation at positions distal to the hydroxyl group. Unlike conventional substitution reactions, which occur at the original or allylic position of a leaving group and typically require preactivation, this strategy directly exploits native alcohols and forges bonds that are remote from the hydroxyl site. The reaction overcomes the intrinsic preference for β-H elimination by selectively promoting β-OH elimination through a novel ligand-enabled process. A bulky 1,3-diketone ligand enhances the oxophilicity of nickel probably via reversible keto-enol tautomerization and orchestrates alkene carbo-nickelation, controlled metal migration, and exclusive β-OH elimination. The method operates under mild and redox neutral conditions with excellent regioselectivity, broad functional-group tolerance, and compatibility with alkenyl alcohols of varying chain lengths.