Nickel-Catalyzed 1,2-Distyrylation of 3-Buten-1-ol.

We report the first nickel-catalyzed 1,2-distyrylation of 3-buten-1-ol that enables the simultaneous incorporation of two distinct styryl groups across a double bond. This transformation employs the hydroxyl group as a native directing group, circumventing the need for an external directing group installation and removal. The reaction proceeds under mild conditions, tolerating a broad range of alkenyl boronates and styryl iodides to afford diverse 1,2-distyrylation products in moderate to good yields. The protocol features broad functional group compatibility, gram-scale scalability, and facile derivatization of the hydroxy moiety. Mechanistic studies support a radical pathway involving a Ni(0)/Ni(I)/Ni(II) catalytic cycle, in which either the neutral hydroxyl group or its in situ-generated alkoxide acts as the directing group.