Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles
A PIII/PV=O-catalyzed C(sp³)–H amination has been realized for (dihydro)benzimidazole synthesis. This work reports: (1) optimization of organophosphorus-catalyzed C(sp³)–H functionalization; (2) scope studies to benzimidazoles by in situ oxidation of the corresponding dihydrobenzimidazole; and (3) i...
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| Format: | Thesis |
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Massachusetts Institute of Technology
2023
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| Online Access: | https://hdl.handle.net/1721.1/147263 |
| _version_ | 1811080723890700288 |
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| author | Pombar, Gisselle |
| author2 | Radosevich, Alexander T. |
| author_facet | Radosevich, Alexander T. Pombar, Gisselle |
| author_sort | Pombar, Gisselle |
| collection | MIT |
| description | A PIII/PV=O-catalyzed C(sp³)–H amination has been realized for (dihydro)benzimidazole synthesis. This work reports: (1) optimization of organophosphorus-catalyzed C(sp³)–H functionalization; (2) scope studies to benzimidazoles by in situ oxidation of the corresponding dihydrobenzimidazole; and (3) insight into the reaction mechanism through in situ spectroscopic monitoring under catalytic conditions and Hammett linear free energy relationship studies. The synthetic method and mechanistic information provide insight into design principles for the expansion of C(sp³)–H functionalization reactions through PIII/PV=O O-atom transfer reactivity. |
| first_indexed | 2024-09-23T11:35:45Z |
| format | Thesis |
| id | mit-1721.1/147263 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T11:35:45Z |
| publishDate | 2023 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/1472632023-01-20T03:38:19Z Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles Pombar, Gisselle Radosevich, Alexander T. Massachusetts Institute of Technology. Department of Chemistry A PIII/PV=O-catalyzed C(sp³)–H amination has been realized for (dihydro)benzimidazole synthesis. This work reports: (1) optimization of organophosphorus-catalyzed C(sp³)–H functionalization; (2) scope studies to benzimidazoles by in situ oxidation of the corresponding dihydrobenzimidazole; and (3) insight into the reaction mechanism through in situ spectroscopic monitoring under catalytic conditions and Hammett linear free energy relationship studies. The synthetic method and mechanistic information provide insight into design principles for the expansion of C(sp³)–H functionalization reactions through PIII/PV=O O-atom transfer reactivity. S.M. 2023-01-19T18:41:17Z 2023-01-19T18:41:17Z 2022-09 2022-10-25T17:27:57.210Z Thesis https://hdl.handle.net/1721.1/147263 In Copyright - Educational Use Permitted Copyright MIT http://rightsstatements.org/page/InC-EDU/1.0/ application/pdf Massachusetts Institute of Technology |
| spellingShingle | Pombar, Gisselle Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles |
| title | Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles |
| title_full | Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles |
| title_fullStr | Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles |
| title_full_unstemmed | Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles |
| title_short | Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles |
| title_sort | studies on organophosphorus catalyzed c sp³ h amination for the synthesis of benzimidazoles |
| url | https://hdl.handle.net/1721.1/147263 |
| work_keys_str_mv | AT pombargisselle studiesonorganophosphoruscatalyzedcsp3haminationforthesynthesisofbenzimidazoles |