Effect of Solvents on Electrogenerated Base-Driven Transfer Hydrogenation Reactions
Transfer hydrogenation is a crucial technology for synthesizing fine chemicals and pharmaceuticals, offering improved safety and convenience over traditional hydrogen methods, although it typically requires external bases. While isopropanol is commonly used as a hydrogen source, methanol is superior...
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| Format: | Article |
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MDPI AG
2025-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/30/4/910 |
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| author | Jing-Wei Zhu Meng-Han Li Feng Zhang Ya-Li Wang Jia-Xing Lu Huan Wang |
| author_facet | Jing-Wei Zhu Meng-Han Li Feng Zhang Ya-Li Wang Jia-Xing Lu Huan Wang |
| author_sort | Jing-Wei Zhu |
| collection | DOAJ |
| description | Transfer hydrogenation is a crucial technology for synthesizing fine chemicals and pharmaceuticals, offering improved safety and convenience over traditional hydrogen methods, although it typically requires external bases. While isopropanol is commonly used as a hydrogen source, methanol is superior but faces challenges due to its high dehydrogenation energy barrier, limiting its use under mild conditions. This study focuses on investigating the differences in the electrogenerated base-driven transfer hydrogenation of aromatic ketones in isopropanol and methanol solvents, using Mn(CO)₅Br and cyclohexanediamine derivatives as the catalyst. The research demonstrates that high enantiomeric excess (ee) values were obtained in isopropanol in the presence of chiral Mn-based catalysts, while only racemic products were observed in methanol. The results indicate a strong dependence of the catalytic pathway on the choice solvent: in isopropanol, the catalyst operates via a metal–ligand cooperative transfer hydrogenation, resulting in high ee values, whereas in methanol, transfer hydrogenation occurs through metal hydride transfer with no stereoselectivity. |
| format | Article |
| id | doaj-art-2daab1d432f9472bb8985a336d99f27f |
| institution | OA Journals |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj-art-2daab1d432f9472bb8985a336d99f27f2025-08-20T02:03:32ZengMDPI AGMolecules1420-30492025-02-0130491010.3390/molecules30040910Effect of Solvents on Electrogenerated Base-Driven Transfer Hydrogenation ReactionsJing-Wei Zhu0Meng-Han Li1Feng Zhang2Ya-Li Wang3Jia-Xing Lu4Huan Wang5Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, ChinaKey Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, ChinaTransfer hydrogenation is a crucial technology for synthesizing fine chemicals and pharmaceuticals, offering improved safety and convenience over traditional hydrogen methods, although it typically requires external bases. While isopropanol is commonly used as a hydrogen source, methanol is superior but faces challenges due to its high dehydrogenation energy barrier, limiting its use under mild conditions. This study focuses on investigating the differences in the electrogenerated base-driven transfer hydrogenation of aromatic ketones in isopropanol and methanol solvents, using Mn(CO)₅Br and cyclohexanediamine derivatives as the catalyst. The research demonstrates that high enantiomeric excess (ee) values were obtained in isopropanol in the presence of chiral Mn-based catalysts, while only racemic products were observed in methanol. The results indicate a strong dependence of the catalytic pathway on the choice solvent: in isopropanol, the catalyst operates via a metal–ligand cooperative transfer hydrogenation, resulting in high ee values, whereas in methanol, transfer hydrogenation occurs through metal hydride transfer with no stereoselectivity.https://www.mdpi.com/1420-3049/30/4/910transfer hydrogenationelectrogenerated basesolvent effectmanganese catalystsaromatic ketones |
| spellingShingle | Jing-Wei Zhu Meng-Han Li Feng Zhang Ya-Li Wang Jia-Xing Lu Huan Wang Effect of Solvents on Electrogenerated Base-Driven Transfer Hydrogenation Reactions Molecules transfer hydrogenation electrogenerated base solvent effect manganese catalysts aromatic ketones |
| title | Effect of Solvents on Electrogenerated Base-Driven Transfer Hydrogenation Reactions |
| title_full | Effect of Solvents on Electrogenerated Base-Driven Transfer Hydrogenation Reactions |
| title_fullStr | Effect of Solvents on Electrogenerated Base-Driven Transfer Hydrogenation Reactions |
| title_full_unstemmed | Effect of Solvents on Electrogenerated Base-Driven Transfer Hydrogenation Reactions |
| title_short | Effect of Solvents on Electrogenerated Base-Driven Transfer Hydrogenation Reactions |
| title_sort | effect of solvents on electrogenerated base driven transfer hydrogenation reactions |
| topic | transfer hydrogenation electrogenerated base solvent effect manganese catalysts aromatic ketones |
| url | https://www.mdpi.com/1420-3049/30/4/910 |
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