Abstract Tricoordinate phosphorus compounds react with a wide variety of double bonds through addition reactions. The dipolar and cyclic products formed are important intermediates in organophosphorus chemistry. We investigated the reactivity between phosphorus triamide 1 and nitrosoarenes and 2-acylpyridines. For sterically congested substrates, the formation of σ5,λ5-phosphorus products is observed. DFT calculations indicate this product is formed through a concerted [4 + 1] mechanism. For less sterically congested substrates, products are observed arising from cleavage of the N = O or C = O bond with formation of a terminal P = O bond and aryl nitrene or carbene migration into a P–N bond of the phosphorus triamide core. DFT calculations are consistent with an initial [2 + 1] addition to phosphorus followed by formal carbene/nitrene migration in these cases. GRAPHICAL ABSTRACT

中文翻译：

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三酰胺磷与亚硝基芳烃和酰基吡啶的加成反应

摘要 三配位磷化合物通过加成反应与多种双键反应。形成的偶极和环状产物是有机磷化学中的重要中间体。我们研究了磷三酰胺 1 与亚硝基芳烃和 2-酰基吡啶之间的反应性。对于空间拥挤的底物，观察到 σ5,λ5-磷产物的形成。DFT 计算表明该产品是通过协调一致的 [4 + 1] 机制形成的。对于空间不太拥挤的底物，观察到产物来自 N = O 或 C = O 键的裂解，形成末端 P = O 键和芳基氮烯或卡宾迁移到三酰胺磷核的 P-N 键。在这些情况下，DFT 计算与最初的 [2 + 1] 添加到磷，然后是正式的卡宾/氮烯迁移一致。图形概要