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 σ 5 , λ 5-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.
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