Efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalysts
Two chiral diamide organocatalysts, N,N'-(oxybis(4,1-phenylene))bis(pyrrolidine-2- carboxamide) (IVa) and N,N'-(methylenebis(4,1-phenylene))bis(pyrrolidine-2-carboxamide) (IVb), were developed to catalyze asymmetric aldol reactions in water with low catalyst loadings ranging from 30% to 10...
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EDP Sciences
2025-01-01
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| Series: | E3S Web of Conferences |
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| Online Access: | https://www.e3s-conferences.org/articles/e3sconf/pdf/2025/01/e3sconf_icegc2024_00103.pdf |
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| author | Benrzeil Hajar Tazi Bouchra Guenoun Farhate |
| author_facet | Benrzeil Hajar Tazi Bouchra Guenoun Farhate |
| author_sort | Benrzeil Hajar |
| collection | DOAJ |
| description | Two chiral diamide organocatalysts, N,N'-(oxybis(4,1-phenylene))bis(pyrrolidine-2- carboxamide) (IVa) and N,N'-(methylenebis(4,1-phenylene))bis(pyrrolidine-2-carboxamide) (IVb), were developed to catalyze asymmetric aldol reactions in water with low catalyst loadings ranging from 30% to 10%. This study aimed to evaluate the influence of chiral concavity of oxygen bridge catalyst IVa on the transition state of aldol reaction in water compared to methylene bridge catalyst IVb in terms of diastereoselectivity, optical purity, reaction time and catalyst loading. The reaction conditions were optimized using p-nitrobenzaldehyde as acceptor and cyclohexanone as donor in the aldol reaction. Oxygen-bridged catalyst IVa showed superior performance to catalyst IVb in water, achieving a reaction time of 28 h, a diastereoselectivity ratio of 78:22 (anti/syn), and an enantiomeric excess of up to 97%. This effect was attributed to the assembly of a chiral cavity facilitated by hydrogen bonds at the oil– water interface and the proximity of the catalytic sites favored by the oxygen bridge of catalyst IVa. Organic solvents, such as DMSO, DCM, and hexane, offered excellent diastereoselectivity, but had reaction times four times longer than those in water. This study highlights the potential of organocatalyst IVa for environmentally friendly asymmetric aldol reactions. |
| format | Article |
| id | doaj-art-2c2d7719ad76490baa7bcfd8ee1bce25 |
| institution | Kabale University |
| issn | 2267-1242 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | EDP Sciences |
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| series | E3S Web of Conferences |
| spelling | doaj-art-2c2d7719ad76490baa7bcfd8ee1bce252025-02-05T10:46:26ZengEDP SciencesE3S Web of Conferences2267-12422025-01-016010010310.1051/e3sconf/202560100103e3sconf_icegc2024_00103Efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalystsBenrzeil Hajar0Tazi Bouchra1Guenoun Farhate2Chemistry-Biology laboratory applied to the environment. Faculty of Science, Moulay Ismail UniversityChemistry Laboratory, DSB, National School of AgricultureChemistry-Biology laboratory applied to the environment. Faculty of Science, Moulay Ismail UniversityTwo chiral diamide organocatalysts, N,N'-(oxybis(4,1-phenylene))bis(pyrrolidine-2- carboxamide) (IVa) and N,N'-(methylenebis(4,1-phenylene))bis(pyrrolidine-2-carboxamide) (IVb), were developed to catalyze asymmetric aldol reactions in water with low catalyst loadings ranging from 30% to 10%. This study aimed to evaluate the influence of chiral concavity of oxygen bridge catalyst IVa on the transition state of aldol reaction in water compared to methylene bridge catalyst IVb in terms of diastereoselectivity, optical purity, reaction time and catalyst loading. The reaction conditions were optimized using p-nitrobenzaldehyde as acceptor and cyclohexanone as donor in the aldol reaction. Oxygen-bridged catalyst IVa showed superior performance to catalyst IVb in water, achieving a reaction time of 28 h, a diastereoselectivity ratio of 78:22 (anti/syn), and an enantiomeric excess of up to 97%. This effect was attributed to the assembly of a chiral cavity facilitated by hydrogen bonds at the oil– water interface and the proximity of the catalytic sites favored by the oxygen bridge of catalyst IVa. Organic solvents, such as DMSO, DCM, and hexane, offered excellent diastereoselectivity, but had reaction times four times longer than those in water. This study highlights the potential of organocatalyst IVa for environmentally friendly asymmetric aldol reactions.https://www.e3s-conferences.org/articles/e3sconf/pdf/2025/01/e3sconf_icegc2024_00103.pdfchiral proline-amidealdol reactionchiral concavityorganocatalysisoxygen-rich catalystcatalytic transition state |
| spellingShingle | Benrzeil Hajar Tazi Bouchra Guenoun Farhate Efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalysts E3S Web of Conferences chiral proline-amide aldol reaction chiral concavity organocatalysis oxygen-rich catalyst catalytic transition state |
| title | Efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalysts |
| title_full | Efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalysts |
| title_fullStr | Efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalysts |
| title_full_unstemmed | Efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalysts |
| title_short | Efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalysts |
| title_sort | efficient direct asymmetric aldol reactions in water using chiral diamide as organocatalysts |
| topic | chiral proline-amide aldol reaction chiral concavity organocatalysis oxygen-rich catalyst catalytic transition state |
| url | https://www.e3s-conferences.org/articles/e3sconf/pdf/2025/01/e3sconf_icegc2024_00103.pdf |
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