Direct conversion of white phosphorus to versatile phosphorus transfer reagents via oxidative onioation

The main feedstock for the value-added phosphorus chemicals used in industry and research is white phosphorus (P₄), from which the key intermediate for forming P(III) compounds is PCl₃. Owing to its high reactivity, syntheses based on PCl₃ are often accompanied by product mixtures and laborious work-up procedures, so an alternative process to form a viable P(III) transfer reagent is desirable. Our concept of oxidative onioation, where white phosphorus is selectively converted into triflate salts of versatile P₁ transfer reagents such as [P(L_N)₃][OTf]₃ (L_N is a cationic, N-based substituent; that is, 4-dimethylaminopyridinio), provides a convenient alternative for the implementation of P-O, P-N and P-C bonds while circumventing the use of PCl₃. We use p-block element compounds of type R_nE (for example, Ph₃As or PhI) to access weak adducts between nitrogen Lewis bases L_N and the corresponding dications [R_nEL_N]²⁺. The proposed equilibrium between [R_nEL_N]²⁺ + L_N and [R_nE(L_N)₂]²⁺ allows for the complete oxidative onioation of all six P-P bonds in P₄ to yield highly reactive and versatile trications [P(L_N)₃]³⁺.