Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification
The utility of unprotected saccharides as chiral auxiliaries in asymmetric synthesis remains largely undeveloped despite their ready availability, configurational diversity, and chiral purity. Here, we disclose an efficient achiral NHC catalytic strategy to regioselectively install racemic α,α-disub...
| Main Authors: | , , , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2024
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/180831 |
| _version_ | 1826122197891022848 |
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| author | Dai, Shuolu Zou, Juan Wang, Haiqi Xu, Min Xu, Erjuan Song, Jia Hong, Yu Li, Shaojun Lv, Wen-Xin Chi, Robin Yonggui |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Dai, Shuolu Zou, Juan Wang, Haiqi Xu, Min Xu, Erjuan Song, Jia Hong, Yu Li, Shaojun Lv, Wen-Xin Chi, Robin Yonggui |
| author_sort | Dai, Shuolu |
| collection | NTU |
| description | The utility of unprotected saccharides as chiral auxiliaries in asymmetric synthesis remains largely undeveloped despite their ready availability, configurational diversity, and chiral purity. Here, we disclose an efficient achiral NHC catalytic strategy to regioselectively install racemic α,α-disubstituted carboxylic esters on specific OH groups of saccharides and simultaneously achieve their dynamic kinetic resolution, which makes unprotected saccharides effective chiral auxiliaries. Multiple controlling parameters, including stereoelectronic and steric effects, are employed to ensure regioselectivity amplification and stereodifferentiation. By varying the structures of NHC catalysts, this strategy is suitable for dynamic kinetic resolution of diverse racemic targets by installing them on different OH sites of structurally diverse unprotected saccharides, greatly expanding the application of saccharides in asymmetric synthesis. |
| first_indexed | 2025-03-09T13:10:38Z |
| format | Journal Article |
| id | ntu-10356/180831 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2025-03-09T13:10:38Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1808312024-10-29T02:35:31Z Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification Dai, Shuolu Zou, Juan Wang, Haiqi Xu, Min Xu, Erjuan Song, Jia Hong, Yu Li, Shaojun Lv, Wen-Xin Chi, Robin Yonggui School of Chemistry, Chemical Engineering and Biotechnology Chemistry Chiral auxiliary Dynamic kinetic resolution The utility of unprotected saccharides as chiral auxiliaries in asymmetric synthesis remains largely undeveloped despite their ready availability, configurational diversity, and chiral purity. Here, we disclose an efficient achiral NHC catalytic strategy to regioselectively install racemic α,α-disubstituted carboxylic esters on specific OH groups of saccharides and simultaneously achieve their dynamic kinetic resolution, which makes unprotected saccharides effective chiral auxiliaries. Multiple controlling parameters, including stereoelectronic and steric effects, are employed to ensure regioselectivity amplification and stereodifferentiation. By varying the structures of NHC catalysts, this strategy is suitable for dynamic kinetic resolution of diverse racemic targets by installing them on different OH sites of structurally diverse unprotected saccharides, greatly expanding the application of saccharides in asymmetric synthesis. Ministry of Education (MOE) Nanyang Technological University National Research Foundation (NRF) We acknowledge financial support from the National Natural Science Foundation of China (U23A20201, 22071036), National Natural Science Fund for Excellent Young Scientists Fund Program (Overseas), the starting grant of Guizhou University [(2024)01], National Key Research and Development Program of China (2022YFD1700300), the Program of Introducing Talents of Discipline to Universities of China (111Program, D20023) at Guizhou University, Frontiers Science enter for Asymmetric Synthesis and Medicinal Molecules, Department of Education, Guizhou Province [Qianjiaohe KY(2020)004], the Central Government Guides Local Science and Technology Development Fund Projects [Qiankehezhon-gyindi (2024) 007, (2023)001], Singapore National Research Foundation under its NRF Competitive Research Program(NRF-CRP22-2019-0002), Ministry of Education, Singapore, under its MOE AcRF Tier 1 Award (RG84/22, RG70/21),MOE AcRF Tier 2 (MOE-T2EP10222-0006), and MOE AcRF Tier 3 Award (MOE2018-T3-1-003), a Chair Professor-ship Grant, and Nanyang Technological University. 2024-10-29T02:35:30Z 2024-10-29T02:35:30Z 2024 Journal Article Dai, S., Zou, J., Wang, H., Xu, M., Xu, E., Song, J., Hong, Y., Li, S., Lv, W. & Chi, R. Y. (2024). Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification. ACS Catalysis, 14(18), 14043-14047. https://dx.doi.org/10.1021/acscatal.4c04076 2155-5435 https://hdl.handle.net/10356/180831 10.1021/acscatal.4c04076 2-s2.0-85204703953 18 14 14043 14047 en NRF-CRP22-2019-0002 RG84/22 RG70/21 MOE-T2EP10222-0006 MOE2018-T3-1-003 ACS Catalysis © 2024 American Chemical Society. All rights reserved. |
| spellingShingle | Chemistry Chiral auxiliary Dynamic kinetic resolution Dai, Shuolu Zou, Juan Wang, Haiqi Xu, Min Xu, Erjuan Song, Jia Hong, Yu Li, Shaojun Lv, Wen-Xin Chi, Robin Yonggui Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification |
| title | Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification |
| title_full | Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification |
| title_fullStr | Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification |
| title_full_unstemmed | Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification |
| title_short | Saccharide-assisted resolution of bioactive chiral carboxylic acids via NHC-catalyzed regioselective transesterification |
| title_sort | saccharide assisted resolution of bioactive chiral carboxylic acids via nhc catalyzed regioselective transesterification |
| topic | Chemistry Chiral auxiliary Dynamic kinetic resolution |
| url | https://hdl.handle.net/10356/180831 |
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