Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines
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-acylpyridine...
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| Format: | Article |
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Taylor & Francis
2020
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| Online Access: | https://hdl.handle.net/1721.1/127806 |
| _version_ | 1826203617084833792 |
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| author | te Grotenhuis, Colet Mattos, Jared T. Radosevich, Alexander T. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry te Grotenhuis, Colet Mattos, Jared T. Radosevich, Alexander T. |
| author_sort | te Grotenhuis, Colet |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T12:40:06Z |
| format | Article |
| id | mit-1721.1/127806 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T12:40:06Z |
| publishDate | 2020 |
| publisher | Taylor & Francis |
| record_format | dspace |
| spelling | mit-1721.1/1278062022-10-01T10:25:48Z Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines te Grotenhuis, Colet Mattos, Jared T. Radosevich, Alexander T. Massachusetts Institute of Technology. Department of Chemistry 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. 2020-10-05T16:41:26Z 2020-10-05T16:41:26Z 2020-09 2020-03 Article http://purl.org/eprint/type/JournalArticle 1042-6507 1563-5325 https://hdl.handle.net/1721.1/127806 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 https://doi.org/10.1080/10426507.2020.1804188 Phosphorus, Sulfur, and Silicon and the Related Elements Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf application/pdf Taylor & Francis Prof. Radosevich |
| spellingShingle | te Grotenhuis, Colet Mattos, Jared T. Radosevich, Alexander T. Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines |
| title | Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines |
| title_full | Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines |
| title_fullStr | Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines |
| title_full_unstemmed | Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines |
| title_short | Addition Reactions of a Phosphorus Triamide to Nitrosoarenes and Acylpyridines |
| title_sort | addition reactions of a phosphorus triamide to nitrosoarenes and acylpyridines |
| url | https://hdl.handle.net/1721.1/127806 |
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