Nickel‐Catalyzed 1,2‐Arylalkenylation of Unactivated Alkenes Enabled by a Native Hydroxy Group

Transition-metal-catalyzed dicarbofunctionalization of alkenes represents a powerful strategy for building molecular complexity in a single step. Here we report an unprecedented nickel-catalyzed 1,2-arylalkenylation of unactivated alkenyl alcohols using alkenyl boronates and aryl iodides. This method uniquely leverages the native hydroxyl group as an intrinsic directing handle, eliminating the need for pre-installed auxiliaries and streamlining the synthesis of structurally diverse alkenol derivatives. The reaction proceeds under mild conditions with broad functional group tolerance and excellent regioselectivity, enabling efficient construction of valuable building blocks. Mechanistic studies, supported by DFT calculations, reveal a Ni(0)/Ni(I)/Ni(II) catalytic cycle probably involving aryl radical intermediates. By exploiting alcohols as directing groups, this work expands the scope of alkene dicarbofunctionalization and provides a versatile platform for late-stage functionalization relevant to pharmaceuticals, agrochemicals, and materials development.