Direct Synthesis of Cyclic Phosphoramides From White Phosphorus Prompted by Dichalcogenides

Abstract

A chlorine‐free approach was developed to synthesize cyclic phosphoramides from white phosphorus (P ₄ ). Using organic disulfides and diphenyl diselenide as both the mediators and reactants, white phosphorus could react with amino alcohols smoothly to generate cyclic phosphoramides in moderate‐to‐good yields (34%–95%). This one‐step approach features mild reaction conditions and a simple operational process without chlorination. Mechanistic studies showed that the P═O double bond in the product was formed via possible bicyclic quaternary phosphonium salt intermediates. In addition, the organic disulfides/diselenides could be recycled without the addition of external oxidants.