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.

The use of mixed aliphatic organozinc reagents in the multicomponent Mannich reaction is described. A large variety of primary, secondary, and tertiary organozinc reagents, secondary amines and aromatic or aliphatic aldehydes could be used for the straightforward preparation of densely substituted amines. The three-component reaction could additionally be performed starting from alkyl halides under reductive (Barbier-type) conditions.