Catalytic, contra-Thermodynamic Positional Alkene Isomerization
The positional isomerization of C═C double bonds is a powerful strategy for the interconversion of alkene regioisomers. However, existing methods provide access to thermodynamically more stable isomers from less stable starting materials. Here, we report the discovery of a dual catalyst system that...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2022
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| Online Access: | https://hdl.handle.net/1721.1/141321 |
| _version_ | 1811093249095368704 |
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| author | Occhialini, Gino Palani, Vignesh Wendlandt, Alison E |
| author_facet | Occhialini, Gino Palani, Vignesh Wendlandt, Alison E |
| author_sort | Occhialini, Gino |
| collection | MIT |
| description | The positional isomerization of C═C double bonds is a powerful strategy for the interconversion of alkene regioisomers. However, existing methods provide access to thermodynamically more stable isomers from less stable starting materials. Here, we report the discovery of a dual catalyst system that promotes contra-thermodynamic positional alkene isomerization under photochemical irradiation, providing access to terminal alkene isomers directly from conjugated, internal alkene starting materials. The utility of the method is demonstrated in the deconjugation of diverse electron-rich/electron-poor alkenes and through strategic application to natural product synthesis. Mechanistic studies are consistent with a regiospecific bimolecular homolytic substitution (SH2') mechanism proceeding through an allyl-cobaloxime intermediate. |
| first_indexed | 2024-09-23T15:42:14Z |
| format | Article |
| id | mit-1721.1/141321 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T15:42:14Z |
| publishDate | 2022 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1413212022-03-22T03:05:13Z Catalytic, contra-Thermodynamic Positional Alkene Isomerization Occhialini, Gino Palani, Vignesh Wendlandt, Alison E The positional isomerization of C═C double bonds is a powerful strategy for the interconversion of alkene regioisomers. However, existing methods provide access to thermodynamically more stable isomers from less stable starting materials. Here, we report the discovery of a dual catalyst system that promotes contra-thermodynamic positional alkene isomerization under photochemical irradiation, providing access to terminal alkene isomers directly from conjugated, internal alkene starting materials. The utility of the method is demonstrated in the deconjugation of diverse electron-rich/electron-poor alkenes and through strategic application to natural product synthesis. Mechanistic studies are consistent with a regiospecific bimolecular homolytic substitution (SH2') mechanism proceeding through an allyl-cobaloxime intermediate. 2022-03-21T14:14:05Z 2022-03-21T14:14:05Z 2022-01-12 2022-03-21T13:59:30Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/141321 Occhialini, Gino, Palani, Vignesh and Wendlandt, Alison E. 2022. "Catalytic, contra-Thermodynamic Positional Alkene Isomerization." Journal of the American Chemical Society, 144 (1). en 10.1021/jacs.1c12043 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) chemRxiv |
| spellingShingle | Occhialini, Gino Palani, Vignesh Wendlandt, Alison E Catalytic, contra-Thermodynamic Positional Alkene Isomerization |
| title | Catalytic, contra-Thermodynamic Positional Alkene Isomerization |
| title_full | Catalytic, contra-Thermodynamic Positional Alkene Isomerization |
| title_fullStr | Catalytic, contra-Thermodynamic Positional Alkene Isomerization |
| title_full_unstemmed | Catalytic, contra-Thermodynamic Positional Alkene Isomerization |
| title_short | Catalytic, contra-Thermodynamic Positional Alkene Isomerization |
| title_sort | catalytic contra thermodynamic positional alkene isomerization |
| url | https://hdl.handle.net/1721.1/141321 |
| work_keys_str_mv | AT occhialinigino catalyticcontrathermodynamicpositionalalkeneisomerization AT palanivignesh catalyticcontrathermodynamicpositionalalkeneisomerization AT wendlandtalisone catalyticcontrathermodynamicpositionalalkeneisomerization |