Direct Photoexcitation Enables Nickel-Catalyzed C(sp ³ )–C(sp ³ ) Coupling of α-Bromonitriles with Alkylzirconocenes

We report a visible-light-mediated nickel-catalyzed C(sp³)-C(sp³) cross-coupling between α-bromonitriles and alkylzirconocene reagents enabled by a direct photoexcitation strategy. Alkyl radicals are generated from <i>in situ</i> formed alkylzirconocenes under visible-light irradiation and efficiently incorporated into a nickel catalytic cycle to forge C(sp³)-C(sp³) bonds under mild conditions. The reaction accommodates a range of α-bromonitriles and alkene-derived alkyl fragments, and its synthetic utility is demonstrated by scale-up experiments and downstream derivatizations.