Transposition of the phosphinoyl groups in the base-induced rearrangements of N,O-bis(diarylphosphinoyl)hydroxylamines

Article abstract of DOI:10.1016/S0040-4039(97)00915-5

Because the N- and O-phosphinoyl groups can change places prior to rearrangement, Ph₂P(O)NHOP(O)Ar₂ and Ar₂P(O)NHOP(O)Ph₂ (Ar = p-tolyl) both give mixtures of two phosphonamidic-phosphimic anhydrides, Ph(PhNH)P(O)OP(O)Ar₂ and Ar(ArNH)P(O)OP(O)Ph₂, on treatment with KOBu(t) in Bu(t)OH. The transposition of the phosphinoyl groups may involve phosphorane intermediates (7 and 9) having the P atom contained within a three-membered ring.