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Addition reactions of a phosphorus triamide to nitrosoarenes and acylpyridines
Authors:Colet te Grotenhuis  Jared T Mattos
Institution:Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA
Abstract: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 Aroyan, C. E.; Dermenci, A.; Miller, S. J. The Rauhut–Currier Reaction: A History and Its Synthetic Application. Tetrahedron 2009, 65, 40694084. DOI: 10.1016/j.tet.2009.02.066.Crossref], Web of Science ®] Google Scholar]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.
Keywords:Acylpyridine  addition reaction  DFT calculations  nitrosoarene  phosphorus
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