Carbene-catalyzed atroposelective synthesis of axially chiral styrenes
Axially chiral styrenes bearing a chiral axis between a sterically non-congested acyclic alkene and an aryl ring are difficult to prepare due to low rotational barrier of the axis. Disclosed here is an N-heterocyclic carbene (NHC) catalytic asymmetric solution to this problem. Our reaction involves...
| Main Authors: | , , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2022
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| Online Access: | https://hdl.handle.net/10356/155056 |
| _version_ | 1826110345077325824 |
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| author | Yan, Jia-Lei Maiti, Rakesh Ren, Shi-Chao Tian, Weiyi Li, Tingting Xu, Jun Mondal, Bivas Jin, Zhichao Chi, Robin Yonggui |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Yan, Jia-Lei Maiti, Rakesh Ren, Shi-Chao Tian, Weiyi Li, Tingting Xu, Jun Mondal, Bivas Jin, Zhichao Chi, Robin Yonggui |
| author_sort | Yan, Jia-Lei |
| collection | NTU |
| description | Axially chiral styrenes bearing a chiral axis between a sterically non-congested acyclic alkene and an aryl ring are difficult to prepare due to low rotational barrier of the axis. Disclosed here is an N-heterocyclic carbene (NHC) catalytic asymmetric solution to this problem. Our reaction involves ynals, sulfinic acids, and phenols as the substrates with an NHC as the catalyst. Key steps involve selective 1,4-addition of sulfinic anion to acetylenic acylazolium intermediate and sequential E-selective protonation to set up the chiral axis. Our reaction affords axially chiral styrenes bearing a chiral axis as the product with up to > 99:1 e.r., > 20:1 E/Z selectivity, and excellent yields. The sulfone and carboxylic ester moieties in our styrene products are common moieties in bioactive molecules and asymmetric catalysis. |
| first_indexed | 2024-10-01T02:32:52Z |
| format | Journal Article |
| id | ntu-10356/155056 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:32:52Z |
| publishDate | 2022 |
| record_format | dspace |
| spelling | ntu-10356/1550562023-02-28T19:57:52Z Carbene-catalyzed atroposelective synthesis of axially chiral styrenes Yan, Jia-Lei Maiti, Rakesh Ren, Shi-Chao Tian, Weiyi Li, Tingting Xu, Jun Mondal, Bivas Jin, Zhichao Chi, Robin Yonggui School of Physical and Mathematical Sciences Science::Chemistry Acetylene Alkene Axially chiral styrenes bearing a chiral axis between a sterically non-congested acyclic alkene and an aryl ring are difficult to prepare due to low rotational barrier of the axis. Disclosed here is an N-heterocyclic carbene (NHC) catalytic asymmetric solution to this problem. Our reaction involves ynals, sulfinic acids, and phenols as the substrates with an NHC as the catalyst. Key steps involve selective 1,4-addition of sulfinic anion to acetylenic acylazolium intermediate and sequential E-selective protonation to set up the chiral axis. Our reaction affords axially chiral styrenes bearing a chiral axis as the product with up to > 99:1 e.r., > 20:1 E/Z selectivity, and excellent yields. The sulfone and carboxylic ester moieties in our styrene products are common moieties in bioactive molecules and asymmetric catalysis. Published version 2022-02-03T08:32:07Z 2022-02-03T08:32:07Z 2022 Journal Article Yan, J., Maiti, R., Ren, S., Tian, W., Li, T., Xu, J., Mondal, B., Jin, Z. & Chi, R. Y. (2022). Carbene-catalyzed atroposelective synthesis of axially chiral styrenes. Nature Communications, 13(1), 84-. https://dx.doi.org/10.1038/s41467-021-27771-x 2041-1723 https://hdl.handle.net/10356/155056 10.1038/s41467-021-27771-x 35013298 2-s2.0-85122879924 1 13 84 en Nature Communications © 2022 The Author(s). This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/ licenses/by/4.0/. application/pdf |
| spellingShingle | Science::Chemistry Acetylene Alkene Yan, Jia-Lei Maiti, Rakesh Ren, Shi-Chao Tian, Weiyi Li, Tingting Xu, Jun Mondal, Bivas Jin, Zhichao Chi, Robin Yonggui Carbene-catalyzed atroposelective synthesis of axially chiral styrenes |
| title | Carbene-catalyzed atroposelective synthesis of axially chiral styrenes |
| title_full | Carbene-catalyzed atroposelective synthesis of axially chiral styrenes |
| title_fullStr | Carbene-catalyzed atroposelective synthesis of axially chiral styrenes |
| title_full_unstemmed | Carbene-catalyzed atroposelective synthesis of axially chiral styrenes |
| title_short | Carbene-catalyzed atroposelective synthesis of axially chiral styrenes |
| title_sort | carbene catalyzed atroposelective synthesis of axially chiral styrenes |
| topic | Science::Chemistry Acetylene Alkene |
| url | https://hdl.handle.net/10356/155056 |
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