Direct Synthesis of Cyclic Phosphoramides from White Phosphorus Prompted by Dichalcogenides

Yu Chen, Yu-Zhong Yang, Peifeng Mei, Xinlei Huangfu,* Yulong Li,* and Wen-Xiong Zhang*

Chem. Eur. J. 2026, 32, e71747.

https://doi.org/10.1002/chem.71747

    A chlorine-free approach was developed to synthesize cyclic phosphoramides from white phosphorus (P₄). 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.