Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines
Author(s)
te Grotenhuis, Colet
Mattos, Jared T.
Radosevich, Alexander T.
Date Issued
September 2020
Journal
Phosphorus, Sulfur, and Silicon and the Related Elements
Publisher
Taylor & Francis
Citation
te Grotenhuis, Colet et al. "Addition reactions of a phosphorus triamide to nitrosoarenes and acylpyridines." Phosphorus, Sulfur, and Silicon and the Related Elements (September 2020): 940-946
Version
Author's final manuscript
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution-Noncommercial-Share Alike
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1080/10426507.2020.1804188
