A highly regioselective O/C phosphorylation of α-chloroketones with trialkyl phosphites was developed in the preparation of enol phosphates and β-ketophosphonates.

Versatile β‐chloro‐α‐hydroxyphosphonates were synthesized in high yields from α‐chloroketones and phosphites based on the efficient control of competitive Pudovik/Arbuzov/Perkow reactions. Triethylamine was found most efficient to catalyze the Pudovik reaction regioselectively under mild solvent‐free conditions. Aliphatic, aromatic, cyclic α‐chloroketones and phosphonites/phosphinites were also applicable to this practical column‐free procedure.