Carbene-catalyzed enantioselective addition of sulfinate to ketones
A carbene-catalyzed enantioselective addition of sulfinate to ketones between 2-benzoylbenzaldehyde and sulfonyl chloride is disclosed. Up to now, the carbon and heteroatom nucleophiles have effectively undergone catalytic enantioselective addition to carbonyl molecules to introduce functionalities...
| 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/10356/179383 |
| _version_ | 1826110506983751680 |
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| author | Deng, Rui Pan, Mingyi Liu, Jianjian Zheng, Pengcheng Chi, Robin Yonggui |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Deng, Rui Pan, Mingyi Liu, Jianjian Zheng, Pengcheng Chi, Robin Yonggui |
| author_sort | Deng, Rui |
| collection | NTU |
| description | A carbene-catalyzed enantioselective addition of sulfinate to ketones between 2-benzoylbenzaldehyde and sulfonyl chloride is disclosed. Up to now, the carbon and heteroatom nucleophiles have effectively undergone catalytic enantioselective addition to carbonyl molecules to introduce functionalities and chirality. Sulfone, as an important class of sulfur-containing functional groups, represents highly valuable motifs in medicines and natural products. It remains undeveloped for the catalytic asymmetric addition of sulfinate to carbonyls. Herein we disclosed the first catalytic enantioselective addition of sulfinate to ketones for the synthesis of sulfones via N-heterocyclic carbene (NHC) catalysis. The sulfonyl chloride behaves both as an oxidant and as a nucleophilic substrate in this carbene-catalyzed process. Experimental studies suggested that the Breslow intermediate can be SET oxidized by sulfonyl chloride to generate the sulfonyl radical. This novel synthetic approach for the asymmetric addition of sulfinate to carbonyls can also be used to modify the commercially available functional molecules. |
| first_indexed | 2024-10-01T02:35:34Z |
| format | Journal Article |
| id | ntu-10356/179383 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:35:34Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1793832024-07-29T05:09:33Z Carbene-catalyzed enantioselective addition of sulfinate to ketones Deng, Rui Pan, Mingyi Liu, Jianjian Zheng, Pengcheng Chi, Robin Yonggui School of Chemistry, Chemical Engineering and Biotechnology Engineering Carbonyl derivative Ketone A carbene-catalyzed enantioselective addition of sulfinate to ketones between 2-benzoylbenzaldehyde and sulfonyl chloride is disclosed. Up to now, the carbon and heteroatom nucleophiles have effectively undergone catalytic enantioselective addition to carbonyl molecules to introduce functionalities and chirality. Sulfone, as an important class of sulfur-containing functional groups, represents highly valuable motifs in medicines and natural products. It remains undeveloped for the catalytic asymmetric addition of sulfinate to carbonyls. Herein we disclosed the first catalytic enantioselective addition of sulfinate to ketones for the synthesis of sulfones via N-heterocyclic carbene (NHC) catalysis. The sulfonyl chloride behaves both as an oxidant and as a nucleophilic substrate in this carbene-catalyzed process. Experimental studies suggested that the Breslow intermediate can be SET oxidized by sulfonyl chloride to generate the sulfonyl radical. This novel synthetic approach for the asymmetric addition of sulfinate to carbonyls can also be used to modify the commercially available functional molecules. Ministry of Education (MOE) Nanyang Technological University National Research Foundation (NRF) We acknowledge funding support from the National Key Research and Development Program of China (2022YFD-1700300), the National Natural Science Foundation of China(32172459, 22061007, 22071036), Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules, Department of Education, Guizhou Province (Qianjiaohe KY number(2020)004), the Science and Technology Department of Guizhou Province (Qiankehejichu-ZK[2021]Key033), the Science and Technology Department of Guizhou Province(Qiankehe-jichu-ZK[2022]zhong dian024), the Program of Introducing Talents of Discipline to Universities of China (111Program, D20023) at Guizhou University, Guizhou University of Traditional Chinese Medicine, Guizhou University (China),Singapore National Research Foundation under its NRF Competitive Research Program (NRF-CRP22-2019-0002), Ministry of Education, Singapore, under its MOE AcRF Tier1 Award (RG84/22, RG70/21), MOE AcRF Tier 2 (MOE-T2EP10222-0006), MOE AcRF Tier 3 Award (MOE2018-T3-1-003), a Chair Professorship Grant, and Nanyang Technological University. 2024-07-29T05:09:33Z 2024-07-29T05:09:33Z 2024 Journal Article Deng, R., Pan, M., Liu, J., Zheng, P. & Chi, R. Y. (2024). Carbene-catalyzed enantioselective addition of sulfinate to ketones. Organic Letters, 26(20), 4394-4399. https://dx.doi.org/10.1021/acs.orglett.4c01473 1523-7060 https://hdl.handle.net/10356/179383 10.1021/acs.orglett.4c01473 38742796 2-s2.0-85193532165 20 26 4394 4399 en NRF-CRP22-2019-0002 RG84/22 RG70/21 MOE-T2EP10222-0006 MOE2018-T3-1-003 Organic Letters © 2024 American Chemical Society. All rights reserved. |
| spellingShingle | Engineering Carbonyl derivative Ketone Deng, Rui Pan, Mingyi Liu, Jianjian Zheng, Pengcheng Chi, Robin Yonggui Carbene-catalyzed enantioselective addition of sulfinate to ketones |
| title | Carbene-catalyzed enantioselective addition of sulfinate to ketones |
| title_full | Carbene-catalyzed enantioselective addition of sulfinate to ketones |
| title_fullStr | Carbene-catalyzed enantioselective addition of sulfinate to ketones |
| title_full_unstemmed | Carbene-catalyzed enantioselective addition of sulfinate to ketones |
| title_short | Carbene-catalyzed enantioselective addition of sulfinate to ketones |
| title_sort | carbene catalyzed enantioselective addition of sulfinate to ketones |
| topic | Engineering Carbonyl derivative Ketone |
| url | https://hdl.handle.net/10356/179383 |
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