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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...

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Autores principales: Yan, Jia-Lei, Maiti, Rakesh, Ren, Shi-Chao, Tian, Weiyi, Li, Tingting, Xu, Jun, Mondal, Bivas, Jin, Zhichao, Chi, Yonggui Robin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8748895/
https://www.ncbi.nlm.nih.gov/pubmed/35013298
http://dx.doi.org/10.1038/s41467-021-27771-x
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author Yan, Jia-Lei
Maiti, Rakesh
Ren, Shi-Chao
Tian, Weiyi
Li, Tingting
Xu, Jun
Mondal, Bivas
Jin, Zhichao
Chi, Yonggui Robin
author_facet Yan, Jia-Lei
Maiti, Rakesh
Ren, Shi-Chao
Tian, Weiyi
Li, Tingting
Xu, Jun
Mondal, Bivas
Jin, Zhichao
Chi, Yonggui Robin
author_sort Yan, Jia-Lei
collection PubMed
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.
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spelling pubmed-87488952022-01-20 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, Yonggui Robin Nat Commun Article 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. Nature Publishing Group UK 2022-01-10 /pmc/articles/PMC8748895/ /pubmed/35013298 http://dx.doi.org/10.1038/s41467-021-27771-x Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access 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/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Yan, Jia-Lei
Maiti, Rakesh
Ren, Shi-Chao
Tian, Weiyi
Li, Tingting
Xu, Jun
Mondal, Bivas
Jin, Zhichao
Chi, Yonggui Robin
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 Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8748895/
https://www.ncbi.nlm.nih.gov/pubmed/35013298
http://dx.doi.org/10.1038/s41467-021-27771-x
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