Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts

Kinetic resolution (KR) of racemic starting materials is a powerful and practical alternative to prepare valuable enantiomerically enriched compounds. A magnesium-catalyzed kinetic resolution based on a designed intramolecular vinylogous Michael reaction is disclosed. Here we show a synergistic cata...

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Autores principales: Li, Dan, Yang, Yuling, Zhang, Minmin, Wang, Linqing, Xu, Yingfan, Yang, Dongxu, Wang, Rui
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7244749/
https://www.ncbi.nlm.nih.gov/pubmed/32444612
http://dx.doi.org/10.1038/s41467-020-16486-0
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author Li, Dan
Yang, Yuling
Zhang, Minmin
Wang, Linqing
Xu, Yingfan
Yang, Dongxu
Wang, Rui
author_facet Li, Dan
Yang, Yuling
Zhang, Minmin
Wang, Linqing
Xu, Yingfan
Yang, Dongxu
Wang, Rui
author_sort Li, Dan
collection PubMed
description Kinetic resolution (KR) of racemic starting materials is a powerful and practical alternative to prepare valuable enantiomerically enriched compounds. A magnesium-catalyzed kinetic resolution based on a designed intramolecular vinylogous Michael reaction is disclosed. Here we show a synergistic catalytic strategy based on the development of chiral ligands. Substrates containing linear allylic ester structures are designed and synthesized to construct key [6.6.5]-tricyclic chiral skeletons via this kinetic resolution process. Detailed mechanistic studies reveal a rational mechanism for the current intramolecular vinylogous KR reaction. The desired direct intramolecular asymmetric vinylogous Michael reaction of linear allylic esters is realized in high efficiency and enantioselectivity with the synergistic catalytic system.
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spelling pubmed-72447492020-06-03 Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts Li, Dan Yang, Yuling Zhang, Minmin Wang, Linqing Xu, Yingfan Yang, Dongxu Wang, Rui Nat Commun Article Kinetic resolution (KR) of racemic starting materials is a powerful and practical alternative to prepare valuable enantiomerically enriched compounds. A magnesium-catalyzed kinetic resolution based on a designed intramolecular vinylogous Michael reaction is disclosed. Here we show a synergistic catalytic strategy based on the development of chiral ligands. Substrates containing linear allylic ester structures are designed and synthesized to construct key [6.6.5]-tricyclic chiral skeletons via this kinetic resolution process. Detailed mechanistic studies reveal a rational mechanism for the current intramolecular vinylogous KR reaction. The desired direct intramolecular asymmetric vinylogous Michael reaction of linear allylic esters is realized in high efficiency and enantioselectivity with the synergistic catalytic system. Nature Publishing Group UK 2020-05-22 /pmc/articles/PMC7244749/ /pubmed/32444612 http://dx.doi.org/10.1038/s41467-020-16486-0 Text en © The Author(s) 2020 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/.
spellingShingle Article
Li, Dan
Yang, Yuling
Zhang, Minmin
Wang, Linqing
Xu, Yingfan
Yang, Dongxu
Wang, Rui
Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts
title Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts
title_full Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts
title_fullStr Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts
title_full_unstemmed Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts
title_short Activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts
title_sort activation of allylic esters in an intramolecular vinylogous kinetic resolution reaction with synergistic magnesium catalysts
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7244749/
https://www.ncbi.nlm.nih.gov/pubmed/32444612
http://dx.doi.org/10.1038/s41467-020-16486-0
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