N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes
N-Heterocyclic carbenes (NHCs) have emerged as powerful organocatalysts in controlling the stereoselectivities of the reaction sites that are remote from the catalyst-binding position. Meanwhile, the construction of a stereogenic center at the δ-position through NHC catalysis remains an unmet goal....
| Main Authors: | , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2024
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| Online Access: | https://hdl.handle.net/10356/174245 |
| _version_ | 1811684659332907008 |
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| author | Peng, Xiaolin Huang, Yixian Wang, Wei Li, Shiguang Hao, Gefei Ren, Shichao Chi, Robin Yonggui |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Peng, Xiaolin Huang, Yixian Wang, Wei Li, Shiguang Hao, Gefei Ren, Shichao Chi, Robin Yonggui |
| author_sort | Peng, Xiaolin |
| collection | NTU |
| description | N-Heterocyclic carbenes (NHCs) have emerged as powerful organocatalysts in controlling the stereoselectivities of the reaction sites that are remote from the catalyst-binding position. Meanwhile, the construction of a stereogenic center at the δ-position through NHC catalysis remains an unmet goal. Herein, we report the NHC-catalyzed enantioselective 1,6-conjugated addition reaction of formyl enynes with nucleophiles through an oxidative LUMO activation strategy. The reaction enables efficient chirality control at the δ-position of the formyl enyne substrates, providing access to high-value-added enantio-enriched pyrano[2,3-b]indole and pyrano[2,3-c]pyrazole derivatives. In addition, central-to-axial chirality transfer through the oxidation of our products was realized, enabling facile access to axially chiral pyrans. |
| first_indexed | 2024-10-01T04:32:09Z |
| format | Journal Article |
| id | ntu-10356/174245 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T04:32:09Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1742452024-03-29T15:31:47Z N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes Peng, Xiaolin Huang, Yixian Wang, Wei Li, Shiguang Hao, Gefei Ren, Shichao Chi, Robin Yonggui School of Chemistry, Chemical Engineering and Biotechnology Chemistry N-heterocyclic carbene Organocatalysis N-Heterocyclic carbenes (NHCs) have emerged as powerful organocatalysts in controlling the stereoselectivities of the reaction sites that are remote from the catalyst-binding position. Meanwhile, the construction of a stereogenic center at the δ-position through NHC catalysis remains an unmet goal. Herein, we report the NHC-catalyzed enantioselective 1,6-conjugated addition reaction of formyl enynes with nucleophiles through an oxidative LUMO activation strategy. The reaction enables efficient chirality control at the δ-position of the formyl enyne substrates, providing access to high-value-added enantio-enriched pyrano[2,3-b]indole and pyrano[2,3-c]pyrazole derivatives. In addition, central-to-axial chirality transfer through the oxidation of our products was realized, enabling facile access to axially chiral pyrans. Ministry of Education (MOE) Nanyang Technological University National Research Foundation (NRF) Submitted/Accepted version We acknowledge financial support from the National Natural Science Foundation of China (22371057, 22371058, 21961006, 32172459, 22371057, and 22071036), the National Key Research and Development Program of China (2022YFD1700300), the Science and Technology Department of Guizhou Province (Qiankehejichu-ZK[2021]Key033), the Program of Introducing Talents of Discipline to Universities of China (111 Program, D20023) at the Guizhou University, Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules, Department of Education, Guizhou Province [Qianjiaohe KY (2020)004], and Guizhou University (China), Singapore National Research Foundation under its NRF Investigatorship (NRF-NRFI2016-06 and U23A20201) and Competitive Research Program (NRF-CRP22-2019-0002), the Ministry of Education, Singapore, under its MOE AcRF Tier 1 Award (RG7/20 and RG70/21), MOE AcRF Tier 2 (MOE2019-T2-2-117), and MOE AcRF Tier 3 Award (MOE2018-T3-1-003), a Chair Professorship Grant, and the Nanyang Technological University, the Central Government Guides Local Science and Technology Development Fund Projects (Qiankehezhongyindi(2023)001), and the National Natural Science Fund for Excellent Young Scientists Fund Program (Overseas), the starting grant of Guizhou University [(2023)29)]. 2024-03-25T02:35:37Z 2024-03-25T02:35:37Z 2024 Journal Article Peng, X., Huang, Y., Wang, W., Li, S., Hao, G., Ren, S. & Chi, R. Y. (2024). N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes. ACS Catalysis, 14(3), 2127-2133. https://dx.doi.org/10.1021/acscatal.3c04733 2155-5435 https://hdl.handle.net/10356/174245 10.1021/acscatal.3c04733 2-s2.0-85184611262 3 14 2127 2133 en NRF-NRFI2016-06 U23A20201 NRF-CRP22-2019-0002 RG7/20 RG70/21 MOE2019-T2-2-117 MOE2018-T3-1-003 ACS Catalysis © 2024 American Chemical Society. All rights reserved. This article may be downloaded for personal use only. Any other use requires prior permission of the copyright holder. The Version of Record is available online at http://doi.org/10.1021/acscatal.3c04733. application/pdf |
| spellingShingle | Chemistry N-heterocyclic carbene Organocatalysis Peng, Xiaolin Huang, Yixian Wang, Wei Li, Shiguang Hao, Gefei Ren, Shichao Chi, Robin Yonggui N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes |
| title | N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes |
| title_full | N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes |
| title_fullStr | N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes |
| title_full_unstemmed | N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes |
| title_short | N-Heterocyclic carbene-catalyzed remote enantioselective C-C bond formation via 1,6-addition with formyl enynes |
| title_sort | n heterocyclic carbene catalyzed remote enantioselective c c bond formation via 1 6 addition with formyl enynes |
| topic | Chemistry N-heterocyclic carbene Organocatalysis |
| url | https://hdl.handle.net/10356/174245 |
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