Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers
The dominated approaches for asymmetric aldol reactions have primarily focused on the aldol carbon-carbon bond-forming events. Here we postulate and develop a new catalytic strategy that seeks to modulate the reaction thermodynamics and control the product enantioselectivities via post-aldol process...
| Main Authors: | , , , , , , , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
| Published: |
2021
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/148221 |
| _version_ | 1826113095395704832 |
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| author | Yang, Xing Majhi, Pankaj Kumar Chai, Huifang Liu, Bin Sun, Jun Liu, Ting Liu, Yonggui Zhou, Liejin Xu, Jun Liu, Jiawei Wang, Dongdong Zhao, Yanli Jin, Zhichao Chi, Robin Yonggui |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Yang, Xing Majhi, Pankaj Kumar Chai, Huifang Liu, Bin Sun, Jun Liu, Ting Liu, Yonggui Zhou, Liejin Xu, Jun Liu, Jiawei Wang, Dongdong Zhao, Yanli Jin, Zhichao Chi, Robin Yonggui |
| author_sort | Yang, Xing |
| collection | NTU |
| description | The dominated approaches for asymmetric aldol reactions have primarily focused on the aldol carbon-carbon bond-forming events. Here we postulate and develop a new catalytic strategy that seeks to modulate the reaction thermodynamics and control the product enantioselectivities via post-aldol processes. Specifically, an NHC catalyst is used to activate a masked enolate substrate (vinyl carbonate) to promote the aldol reaction in a non-enantioselective manner. This reversible aldol event is subsequently followed by an enantioselective acylative kinetic resolution that is mediated by the same (chiral) NHC catalyst without introducing any additional substance. This post-aldol process takes care of the enantioselectivity issues and drives the otherwise reversible aldol reaction toward a complete conversion. The acylated aldol products bearing quaternary/tetrasubstituted carbon stereogenic centers are formed in good yields and high optical purities. |
| first_indexed | 2024-10-01T03:17:54Z |
| format | Journal Article |
| id | ntu-10356/148221 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:17:54Z |
| publishDate | 2021 |
| record_format | dspace |
| spelling | ntu-10356/1482212023-02-28T19:59:01Z Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers Yang, Xing Majhi, Pankaj Kumar Chai, Huifang Liu, Bin Sun, Jun Liu, Ting Liu, Yonggui Zhou, Liejin Xu, Jun Liu, Jiawei Wang, Dongdong Zhao, Yanli Jin, Zhichao Chi, Robin Yonggui School of Physical and Mathematical Sciences Science::Chemistry Acylation Aldol Reaction The dominated approaches for asymmetric aldol reactions have primarily focused on the aldol carbon-carbon bond-forming events. Here we postulate and develop a new catalytic strategy that seeks to modulate the reaction thermodynamics and control the product enantioselectivities via post-aldol processes. Specifically, an NHC catalyst is used to activate a masked enolate substrate (vinyl carbonate) to promote the aldol reaction in a non-enantioselective manner. This reversible aldol event is subsequently followed by an enantioselective acylative kinetic resolution that is mediated by the same (chiral) NHC catalyst without introducing any additional substance. This post-aldol process takes care of the enantioselectivity issues and drives the otherwise reversible aldol reaction toward a complete conversion. The acylated aldol products bearing quaternary/tetrasubstituted carbon stereogenic centers are formed in good yields and high optical purities. Ministry of Education (MOE) National Research Foundation (NRF) Accepted version 2021-05-31T07:55:01Z 2021-05-31T07:55:01Z 2021 Journal Article Yang, X., Majhi, P. K., Chai, H., Liu, B., Sun, J., Liu, T., Liu, Y., Zhou, L., Xu, J., Liu, J., Wang, D., Zhao, Y., Jin, Z. & Chi, R. Y. (2021). Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers. Angewandte Chemie International Edition, 133(1), 161-167. https://dx.doi.org/10.1002/anie.202008369 1521-3773 0000-0003-0573-257X https://hdl.handle.net/10356/148221 10.1002/anie.202008369 32931603 2-s2.0-85096722882 1 133 161 167 en Angewandte Chemie International Edition This is the peer reviewed version of the following article: Yang, X., Majhi, P. K., Chai, H., Liu, B., Sun, J., Liu, T., Liu, Y., Zhou, L., Xu, J., Liu, J., Wang, D., Zhao, Y., Jin, Z. & Chi, R. Y. (2021). Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers. Angewandte Chemie International Edition, 133(1), 161-167. https://dx.doi.org/10.1002/anie.202008369 , which has been published in final form at https://doi.org/10.1002/ange.202008369. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. application/pdf |
| spellingShingle | Science::Chemistry Acylation Aldol Reaction Yang, Xing Majhi, Pankaj Kumar Chai, Huifang Liu, Bin Sun, Jun Liu, Ting Liu, Yonggui Zhou, Liejin Xu, Jun Liu, Jiawei Wang, Dongdong Zhao, Yanli Jin, Zhichao Chi, Robin Yonggui Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers |
| title | Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers |
| title_full | Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers |
| title_fullStr | Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers |
| title_full_unstemmed | Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers |
| title_short | Carbene-catalyzed enantioselective aldol reaction : post-aldol stereochemistry control and formation of quaternary stereogenic centers |
| title_sort | carbene catalyzed enantioselective aldol reaction post aldol stereochemistry control and formation of quaternary stereogenic centers |
| topic | Science::Chemistry Acylation Aldol Reaction |
| url | https://hdl.handle.net/10356/148221 |
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