Recent advances in electrochemical synthesis of phosphorylated organic compounds from P-H reagents.

Organophosphorus compounds constitute an important class of phosphorus-containing molecules that are widely encountered in agrochemicals, pharmaceuticals, functional materials, and ligand frameworks. Consequently, the development of green and efficient methods for their synthesis has attracted considerable attention from the synthetic community. This review systematically summarizes methodological advances from 2020 to 2025 in the electrochemical synthesis of organophosphorus compounds from readily accessible P-H reagents, including dialkyl phosphonates and diphenylphosphine oxides, with selected early 2026 publications also included to ensure comprehensive coverage of the field. The content is organized into four main sections according to bond-forming patterns: P-C, P-N, P-O, and P-X (X = S, Se, F) bond formation. Mechanistically, these reactions are broadly classified into three pathways: (1) direct nucleophilic attack of P-H reagents on electrochemically generated electrophilic intermediates; (2) iodide-mediated processes involving formation of highly electrophilic phosphorus intermediates; and (3) radical pathways featuring phosphorus-centered radicals. Finally, current challenges and future opportunities are discussed.