78 / 2023-09-15 23:50:18

Redox-neutral activation of primary and secondary phosphate sources

Organophosphorus Chemistry,Sustainable Synthesis,Redox-neutral activation,Phosphorylation

New Technologies in Phosphorus Chemistry > 1) New reagents and methods in organophosphorus Chemistry

Phosphorus and its derivatives are crucial components in biological systems and find diverse applications in both life sciences and material-oriented fields. Despite their significance, the current method for synthesizing phosphorus-based fine and bulk chemicals is inefficient and wasteful, relying on a redox detour from primary phosphate (P^V) sources through elemental white phosphorus and its conversion via (oxy)chlorination to produce PCl₃, PCl₅ and POCl₃. This energy-intensive process renders it unsustainable in the long term, necessitating a comprehensive reevaluation of the synthetic route to enhance the efficiency and sustainability of fine and bulk chemical production.

Building upon previous research regarding the deoxygenation of arsine oxides, we introduce a novel approach employing trifluoromethanesulfonic anhydride (Tf₂O) and pyridine to directly cleave P–O bonds in ubiquitous P^V sources. This innovative method results in the formation of a highly versatile PO₂⁺ phosphorylation agent 1[OTf], offering an economical and redox-neutral pathway for synthesizing various P^V chemicals using low-cost phosphoric acid and other phosphate sources. Furthermore, it provides an entrance for the synthesis of intriguing molecules, such as the azidophosphate 2.