Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation
A catalytic method for the direct electrophilic cyanation of C(sp²)–H nucleophiles with sodium cyanate (NaOCN) is reported. Mechanistic experiments show that under solid-liquid phase transfer, an inorganic cyanate is activated by halide displacement on a halophosphonium. Redox catalysis is enabled b...
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| Format: | Thesis |
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Massachusetts Institute of Technology
2024
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| Online Access: | https://hdl.handle.net/1721.1/157726 |
| _version_ | 1824458068914601984 |
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| author | Hu, Shicheng |
| author2 | Radosevich, Alexander T. |
| author_facet | Radosevich, Alexander T. Hu, Shicheng |
| author_sort | Hu, Shicheng |
| collection | MIT |
| description | A catalytic method for the direct electrophilic cyanation of C(sp²)–H nucleophiles with sodium cyanate (NaOCN) is reported. Mechanistic experiments show that under solid-liquid phase transfer, an inorganic cyanate is activated by halide displacement on a halophosphonium. Redox catalysis is enabled by the usage of a strained phosphine (phosphetane) so that catalyst turnover from phosphine oxide to phosphine can be easily achieved by the usage of a terminal hydrosilane reductant. These results demonstrate the feasibility of deoxyfunctionalization of insoluble inorganic salts by Pᴵᴵᴵ/Pⱽ=O catalyzed phase transfer activation, as exemplified by C(sp²)–H cyanation with NaOCN as the “CN⁺” source. |
| first_indexed | 2025-02-19T04:20:01Z |
| format | Thesis |
| id | mit-1721.1/157726 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2025-02-19T04:20:01Z |
| publishDate | 2024 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/1577262024-12-03T03:41:14Z Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation Hu, Shicheng Radosevich, Alexander T. Massachusetts Institute of Technology. Department of Chemistry A catalytic method for the direct electrophilic cyanation of C(sp²)–H nucleophiles with sodium cyanate (NaOCN) is reported. Mechanistic experiments show that under solid-liquid phase transfer, an inorganic cyanate is activated by halide displacement on a halophosphonium. Redox catalysis is enabled by the usage of a strained phosphine (phosphetane) so that catalyst turnover from phosphine oxide to phosphine can be easily achieved by the usage of a terminal hydrosilane reductant. These results demonstrate the feasibility of deoxyfunctionalization of insoluble inorganic salts by Pᴵᴵᴵ/Pⱽ=O catalyzed phase transfer activation, as exemplified by C(sp²)–H cyanation with NaOCN as the “CN⁺” source. S.B. 2024-12-02T21:15:20Z 2024-12-02T21:15:20Z 2024-05 2024-11-18T19:27:25.107Z Thesis https://hdl.handle.net/1721.1/157726 In Copyright - Educational Use Permitted Copyright retained by author(s) https://rightsstatements.org/page/InC-EDU/1.0/ application/pdf Massachusetts Institute of Technology |
| spellingShingle | Hu, Shicheng Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation |
| title | Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation |
| title_full | Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation |
| title_fullStr | Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation |
| title_full_unstemmed | Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation |
| title_short | Electrophilic C(sp²)–H Cyanation with Inorganic Cyanate (OCN⁻) by Pᴵᴵᴵ/Pⱽ=O-Catalyzed Phase Transfer Activation |
| title_sort | electrophilic c sp² h cyanation with inorganic cyanate ocn⁻ by pᴵᴵᴵ pⱽ o catalyzed phase transfer activation |
| url | https://hdl.handle.net/1721.1/157726 |
| work_keys_str_mv | AT hushicheng electrophiliccsp2hcyanationwithinorganiccyanateocnbypiiipvocatalyzedphasetransferactivation |