Formal C-H alkylation of (hetero)arenes via a one-pot halogenation and nickel-catalyzed cross-electrophile coupling strategy.

Direct C(sp2)-C(sp3) bond formation via arene C-H alkylation remains a highly desired transformation in organic synthesis. Herein, we describe a versatile one-pot protocol that merges I2/Selectfluor-mediated in situ C-H iodination with nickel-catalyzed reductive cross-electrophile coupling (XEC) to achieve formal C-H alkylation of a broad array of (hetero)arenes. This approach features broad substrate scope and excellent functional group tolerance, enabling effective late-stage alkylation of a number of pharmaceutically relevant scaffolds. Furthermore, the ability to perform sequential alkylation at multiple sites of simple aromatics highlights the potential applications of this protocol in synthetic chemistry.