P–N and P=N bonds play important roles in the design and synthesis of functional molecules such as bioactive compounds and organic ligands for catalysis. Existing methods for P–N coupling mostly rely on Staudinger condensation or nucleophilic substitution between phosphorus electrophiles and amine nucleophiles. Herein, we report a nitrene-mediated intermolecular P–N coupling reaction between various phosphorus nucleophiles and dioxazolones under simple iron-catalyzed conditions. These reactions offer an efficient, versatile, and broadly applicable method for synthesis of a range of N–P compounds, including amidophosphines, iminophosphonamides, phosphinamides, aminophosphines, and iminophosphoranes, from readily available precursors under mild conditions.

P-N 和 P=N 键在功能分子（如生物活性化合物和催化有机配体）的设计和合成中起着重要作用。现有的 P-N 偶联方法主要依赖于磷亲电试剂和胺亲核试剂之间的施陶丁格缩合或亲核取代。在此，我们报告了在简单的铁催化条件下各种磷亲核试剂和二恶唑酮之间的氮烯介导的分子间 P-N 偶联反应。这些反应提供了一种高效、通用和广泛适用的方法，用于在温和条件下从容易获得的前体合成一系列 N-P 化合物，包括酰胺膦、亚氨基膦酰胺、膦酰胺、氨基膦和亚氨基膦。