P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines
An organophosphorus-catalyzed method for the synthesis of unsymmetrical hydrazines by cross-selective intermolecular N-N reductive coupling is reported. This method employs a small ring phosphacycle (phosphetane) catalyst together with hydrosilane as the terminal reductant to drive reductive couplin...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
| Published: |
American Chemical Society (ACS)
2022
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| Online Access: | https://hdl.handle.net/1721.1/145514 |
| _version_ | 1826191338790453248 |
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| author | Li, Gen Miller, Steven P Radosevich, Alexander T |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Li, Gen Miller, Steven P Radosevich, Alexander T |
| author_sort | Li, Gen |
| collection | MIT |
| description | An organophosphorus-catalyzed method for the synthesis of unsymmetrical hydrazines by cross-selective intermolecular N-N reductive coupling is reported. This method employs a small ring phosphacycle (phosphetane) catalyst together with hydrosilane as the terminal reductant to drive reductive coupling of nitroarenes and anilines with good chemoselectivity and functional group tolerance. Mechanistic investigations support an autotandem catalytic reaction cascade in which the organophosphorus catalyst drives two sequential and mechanistically distinct reduction events via PIII/PV═O cycling in order to furnish the target N-N bond. |
| first_indexed | 2024-09-23T08:54:22Z |
| format | Article |
| id | mit-1721.1/145514 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T08:54:22Z |
| publishDate | 2022 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1455142022-09-26T09:06:49Z P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines Li, Gen Miller, Steven P Radosevich, Alexander T Massachusetts Institute of Technology. Department of Chemistry An organophosphorus-catalyzed method for the synthesis of unsymmetrical hydrazines by cross-selective intermolecular N-N reductive coupling is reported. This method employs a small ring phosphacycle (phosphetane) catalyst together with hydrosilane as the terminal reductant to drive reductive coupling of nitroarenes and anilines with good chemoselectivity and functional group tolerance. Mechanistic investigations support an autotandem catalytic reaction cascade in which the organophosphorus catalyst drives two sequential and mechanistically distinct reduction events via PIII/PV═O cycling in order to furnish the target N-N bond. 2022-09-20T12:46:55Z 2022-09-20T12:46:55Z 2021 2022-09-20T12:40:46Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/145514 Li, Gen, Miller, Steven P and Radosevich, Alexander T. 2021. "P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines." Journal of the American Chemical Society, 143 (36). en 10.1021/JACS.1C07272 Journal of the American Chemical Society Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | Li, Gen Miller, Steven P Radosevich, Alexander T P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines |
| title | P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines |
| title_full | P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines |
| title_fullStr | P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines |
| title_full_unstemmed | P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines |
| title_short | P III /P V ═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines |
| title_sort | p iii p v ═o catalyzed intermolecular n n bond formation cross selective reductive coupling of nitroarenes and anilines |
| url | https://hdl.handle.net/1721.1/145514 |
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