Synthesis of Phosphinic Amides from Chlorophosphines and Hydroxyl Amines via P(III) to P(V) Rearrangement

Phosphoranyl radicals are essential mediators to bring about new radicals but often produce a stoichiometric amount of phosphine oxide/sulfide waste. Herein, we devised a phosphorus-containing species as a radical precursor, but without the generation of phosphorus waste. Accordingly, a catalyst-free synthesis of phosphinic amides from hydroxyl amines and chlorophosphines via P(III) to P(V) rearrangement is described. Mechanistically, it may involve the initial formation of a R₂N-O-PR₂ species that undergoes homolysis of N-O bonds and subsequent radical recombination.