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Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes

Recently, transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo- and heterocycles. However, all these reactions rely on facially selective arylmetalation of the pendant olefinic unit. Here, we succe...

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Autores principales: Lan, Yun, Wang, Chuan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814080/
https://www.ncbi.nlm.nih.gov/pubmed/36703467
http://dx.doi.org/10.1038/s42004-020-0292-3
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author Lan, Yun
Wang, Chuan
author_facet Lan, Yun
Wang, Chuan
author_sort Lan, Yun
collection PubMed
description Recently, transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo- and heterocycles. However, all these reactions rely on facially selective arylmetalation of the pendant olefinic unit. Here, we successfully apply acylnickelation as the enantiodetermining step in the asymmetric nickel-catalyzed reductive carbo-acylation of aryl carbamic chloride-tethered alkenes with primary and secondary alkyl iodides as well as benzyl chlorides as the coupling partners, using manganese as a reducing agent. By circumventing the use of pre-generated organometallics, this reductive strategy enables the synthesis of diverse enantioenriched oxindoles bearing a quaternary stereogenic center under mild reaction conditions with high tolerance of a broad range of functional moieties.
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spelling pubmed-98140802023-01-10 Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes Lan, Yun Wang, Chuan Commun Chem Article Recently, transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo- and heterocycles. However, all these reactions rely on facially selective arylmetalation of the pendant olefinic unit. Here, we successfully apply acylnickelation as the enantiodetermining step in the asymmetric nickel-catalyzed reductive carbo-acylation of aryl carbamic chloride-tethered alkenes with primary and secondary alkyl iodides as well as benzyl chlorides as the coupling partners, using manganese as a reducing agent. By circumventing the use of pre-generated organometallics, this reductive strategy enables the synthesis of diverse enantioenriched oxindoles bearing a quaternary stereogenic center under mild reaction conditions with high tolerance of a broad range of functional moieties. Nature Publishing Group UK 2020-04-03 /pmc/articles/PMC9814080/ /pubmed/36703467 http://dx.doi.org/10.1038/s42004-020-0292-3 Text en © The Author(s) 2020 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
Lan, Yun
Wang, Chuan
Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes
title Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes
title_full Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes
title_fullStr Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes
title_full_unstemmed Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes
title_short Nickel-catalyzed enantioselective reductive carbo-acylation of alkenes
title_sort nickel-catalyzed enantioselective reductive carbo-acylation of alkenes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814080/
https://www.ncbi.nlm.nih.gov/pubmed/36703467
http://dx.doi.org/10.1038/s42004-020-0292-3
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