Addition reactions of a phosphorus triamide to nitrosoarenes and acylpyridines
Addition reactions of a phosphorus triamide to nitrosoarenes and acylpyridines
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DOI：
10.1080/10426507.2020.1804188
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发表时间：
2020-09
期刊：
影响因子：
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通讯作者：
Colet te Grotenhuis;J. Mattos;A. Radosevich
中科院分区：
文献类型：
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作者：
Colet te Grotenhuis;J. Mattos;A. Radosevich
摘要三配位磷化合物通过加成反应与多种双键发生反应。形成的偶极和环状产物是有机磷化学的重要中间体。我们研究了磷酰三胺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计算表明该产物是通过[4 + 1]协同机制生成的。对于空间位阻较小的底物，观察到由N = O或C = O键裂解产生的产物，并形成末端P = O键和芳基氮宾或卡宾迁移到磷三酰胺核心的P-N键中。DFT计算是一致的初始[2 + 1]除了磷，然后在这些情况下，正式的卡宾/氮烯迁移。图形摘要
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