Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis
A main group-catalyzed method for the synthesis of aryl- and heteroarylamines by intermolecular C-N coupling is reported. The method employs a small-ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane) and a terminal hydrosilane reductant (phenylsilane) to drive reductive intermo...
| Main Authors: | , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
American Chemical Society (ACS)
2020
|
| Online Access: | https://hdl.handle.net/1721.1/123674 |
| _version_ | 1811082527524257792 |
|---|---|
| author | Nykaza, Trevor Vincent Cooper, Julian Colton Li, Gen Mahieu, Nolwenn Ramirez, Antonio Luzung, Michael R. Radosevich, Alexander T. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Nykaza, Trevor Vincent Cooper, Julian Colton Li, Gen Mahieu, Nolwenn Ramirez, Antonio Luzung, Michael R. Radosevich, Alexander T. |
| author_sort | Nykaza, Trevor Vincent |
| collection | MIT |
| description | A main group-catalyzed method for the synthesis of aryl- and heteroarylamines by intermolecular C-N coupling is reported. The method employs a small-ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane) and a terminal hydrosilane reductant (phenylsilane) to drive reductive intermolecular coupling of nitro(hetero)arenes with boronic acids. Applications to the construction of both C[subscript sp2]-N (from arylboronic acids) and C[subscript sp3]–N bonds (from alkylboronic acids) are demonstrated; the reaction is stereospecific with respect to C[subscript sp3]-N bond formation. The method constitutes a new route from readily available building blocks to valuable nitrogen-containing products with complementarity in both scope and chemoselectivity to existing catalytic C-N coupling methods. Keywords: functionalization; catalysts; coupling reactions; chemical reactions; cyclization |
| first_indexed | 2024-09-23T12:04:49Z |
| format | Article |
| id | mit-1721.1/123674 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T12:04:49Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1236742022-10-01T08:01:51Z Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis Nykaza, Trevor Vincent Cooper, Julian Colton Li, Gen Mahieu, Nolwenn Ramirez, Antonio Luzung, Michael R. Radosevich, Alexander T. Massachusetts Institute of Technology. Department of Chemistry A main group-catalyzed method for the synthesis of aryl- and heteroarylamines by intermolecular C-N coupling is reported. The method employs a small-ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane) and a terminal hydrosilane reductant (phenylsilane) to drive reductive intermolecular coupling of nitro(hetero)arenes with boronic acids. Applications to the construction of both C[subscript sp2]-N (from arylboronic acids) and C[subscript sp3]–N bonds (from alkylboronic acids) are demonstrated; the reaction is stereospecific with respect to C[subscript sp3]-N bond formation. The method constitutes a new route from readily available building blocks to valuable nitrogen-containing products with complementarity in both scope and chemoselectivity to existing catalytic C-N coupling methods. Keywords: functionalization; catalysts; coupling reactions; chemical reactions; cyclization 2020-01-24T15:44:55Z 2020-01-24T15:44:55Z 2018-10-29 2018-10-06 2020-01-06T17:31:57Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 https://hdl.handle.net/1721.1/123674 Nykaza, Trevor V. et al. "Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis." Journal of the American Chemical Society 140, 45 (2018): 15200-15205 © 2018 American Chemical Society en http://dx.doi.org/10.1021/jacs.8b10769 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | Nykaza, Trevor Vincent Cooper, Julian Colton Li, Gen Mahieu, Nolwenn Ramirez, Antonio Luzung, Michael R. Radosevich, Alexander T. Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis |
| title | Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis |
| title_full | Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis |
| title_fullStr | Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis |
| title_full_unstemmed | Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis |
| title_short | Intermolecular Reductive C–N Cross Coupling of Nitroarenes and Boronic Acids by P[superscript III]/P[superscript V]═O Catalysis |
| title_sort | intermolecular reductive c n cross coupling of nitroarenes and boronic acids by p superscript iii p superscript v ═o catalysis |
| url | https://hdl.handle.net/1721.1/123674 |
| work_keys_str_mv | AT nykazatrevorvincent intermolecularreductivecncrosscouplingofnitroarenesandboronicacidsbypsuperscriptiiipsuperscriptvocatalysis AT cooperjuliancolton intermolecularreductivecncrosscouplingofnitroarenesandboronicacidsbypsuperscriptiiipsuperscriptvocatalysis AT ligen intermolecularreductivecncrosscouplingofnitroarenesandboronicacidsbypsuperscriptiiipsuperscriptvocatalysis AT mahieunolwenn intermolecularreductivecncrosscouplingofnitroarenesandboronicacidsbypsuperscriptiiipsuperscriptvocatalysis AT ramirezantonio intermolecularreductivecncrosscouplingofnitroarenesandboronicacidsbypsuperscriptiiipsuperscriptvocatalysis AT luzungmichaelr intermolecularreductivecncrosscouplingofnitroarenesandboronicacidsbypsuperscriptiiipsuperscriptvocatalysis AT radosevichalexandert intermolecularreductivecncrosscouplingofnitroarenesandboronicacidsbypsuperscriptiiipsuperscriptvocatalysis |