Facile Synthesis of H-Phosphinates from P(OR)₃ or ClP(OR)₂ via SiO₂-Promoted Hydrolysis

H-Phosphinates represent a valuable class of organophosphorus building blocks and catalytic ligands. The existing synthetic approaches are generally associated with the use of strong acids, the need for meticulous treatment of intermediates, and the limitation of only P-aryl introductions. Following a comprehensive investigation into the unexpected SiO₂-promoted hydrolysis observed during the chromatography workup of the crude R'P(OR)₂ intermediates, we have developed an extremely simple and general synthetic route to H-phosphinates from commercially available Grignard reagents and P(OR)₃. An alternative approach involved the use of ClP(OR)₂ in place of P(OR)₃, which proved to be a valuable strategy for the preparation of sterically hindered ArMgBr substrates bearing bulky ortho-substituted motifs. A library of 36 structurally diverse P-(cyclo)alkyl and P-(hetero)aryl H-phosphinates was thus obtained in moderate to high yields using this practical protocol. Furthermore, the CuCl₂-mediated P(O)-H bond derivations were also examined, resulting in the formation of the corresponding EtOPhP(O)-X (X = O, N, S) compounds in nearly quantitative yields.