Bridging Homogeneous and Heterogeneous Catalysis: Ni@CPOL-dppp&PPh3-Catalyzed Symmetric H-Phosphonate Diester Synthesis from Sodium Hypophosphite

The biological importance and practical significance of H-phosphonate diesters and their analogues have been the major driving forces for research in various areas of synthetic organic phosphorus chemistry. However, establishment of a gentle and environmentally friendly method to avoid use of toxic PCl 3 is still the biggest challenge in this area. As potential alternatives to PCl 3, we studied the progress in the conversion of cheap and green inorganic salt sodium hypophosphite (NaH 2 PO 2 ) and alcohol into various H-phosphonate diesters [(RO) 2 P(O)H] with the release of H 2 by using the heterogeneous single-atom site Ni@CPOL-dppp&PPh 3 catalyst. Remarkably, the catalyst exhibited outstanding catalytic performance, allowing for the efficient conversion of a wide range of various alcohols to their corresponding H-phosphonate diesters in good to high yields. This new route completely avoids the use of phosphorus trichloride (PCl 3 ) and promises a convenient real process for making H-phosphonate diesters in industry and laboratory. Moreover, the present study provides meaningful insights into the development of well-defined heterogeneous catalysts guided by homogeneous catalysis.