Photoelectrochemical Iron-Nickel Synergistic Catalysis for C(sp3)-H and Dehydroxymethylative Acylation.

We developed an iron-nickel dual-catalytic system for efficient C(sp3)-H activation acylation of hydrocarbons and carboxylic acids under photoelectrochemical conditions. This system is based on ligand-to-metal charge transfer-mediated direct hydrogen atom transfer and is applicable to inert C(sp3)-H-containing compounds. It also enables dehydroxymethylative acylation of alcohols, both these two reactions demonstrating broad substrate scope and unconventional chemoselectivity. Gram-scale synthesis, flow chemistry, and mechanistic studies highlight its potential in sustainable C(acyl)-C bond formation.