Electrochemical C(sp2)−N couplings mediated by nickel salts generated from the sacrificial anode has been described for the first time. In this approach, the sacrificial nickel anode is employed as the sole source of nickel and the process, operationally simple to set up, enables the preparation of functionalized arylamine derivatives with moderate to good yields, under mild reaction conditions and without additional ligand. A cooperative process between the two electrodes is involved in the proposed mechanism.

A mild and useful nickel‐catalyzed electrochemical phosphonylation of aryl and vinyl bromides is described. We show that alkyl H‐phenylphosphinates can be coupled electrochemically with functionalized aryl and vinyl bromides using very simple conditions (Fe/Ni anode, bench‐stable nickel pre‐catalyst, undivided cell, galvanostatic electrolysis) to furnish the corresponding aryl and vinyl phosphinates in satisfactory to good yields. Couplings can also be applied to heteroaromatic bromides with some limitations like increased propensity to hydro‐dehalogenation.