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Asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution

An iridium catalyzed asymmetric hydrogenation of racemic exocyclic γ,δ-unsaturated β-ketoesters via dynamic kinetic resolution to functionalized chiral allylic alcohols was developed. With the chiral spiro iridium catalysts Ir-SpiroPAP, a series of racemic exocyclic γ,δ-unsaturated β-ketoesters bear...

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Autores principales: Bin, Huai-Yu, Cheng, Li, Wu, Xiong, Zhu, Chang-Liang, Yang, Xiao-Hui, Xie, Jian-Hua, Zhou, Qi-Lin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8188505/
https://www.ncbi.nlm.nih.gov/pubmed/34168833
http://dx.doi.org/10.1039/d1sc02044g
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author Bin, Huai-Yu
Cheng, Li
Wu, Xiong
Zhu, Chang-Liang
Yang, Xiao-Hui
Xie, Jian-Hua
Zhou, Qi-Lin
author_facet Bin, Huai-Yu
Cheng, Li
Wu, Xiong
Zhu, Chang-Liang
Yang, Xiao-Hui
Xie, Jian-Hua
Zhou, Qi-Lin
author_sort Bin, Huai-Yu
collection PubMed
description An iridium catalyzed asymmetric hydrogenation of racemic exocyclic γ,δ-unsaturated β-ketoesters via dynamic kinetic resolution to functionalized chiral allylic alcohols was developed. With the chiral spiro iridium catalysts Ir-SpiroPAP, a series of racemic exocyclic γ,δ-unsaturated β-ketoesters bearing a five-, six-, or seven-membered ring were hydrogenated to the corresponding functionalized chiral allylic alcohols in high yields with good to excellent enantioselectivities (87 to >99% ee) and cis-selectivities (93 : 7 to >99 : 1). The origin of the excellent stereoselectivity was also rationalized by density functional theory calculations. Furthermore, this protocol could be performed on gram scale and at a lower catalyst loading (0.002 mol%) without the loss of reactivity and enantioselectivity, and has been successfully applied in the enantioselective synthesis of chiral carbocyclic δ-amino esters and the β-galactosidase inhibitor isogalactofagomine.
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spelling pubmed-81885052021-06-23 Asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution Bin, Huai-Yu Cheng, Li Wu, Xiong Zhu, Chang-Liang Yang, Xiao-Hui Xie, Jian-Hua Zhou, Qi-Lin Chem Sci Chemistry An iridium catalyzed asymmetric hydrogenation of racemic exocyclic γ,δ-unsaturated β-ketoesters via dynamic kinetic resolution to functionalized chiral allylic alcohols was developed. With the chiral spiro iridium catalysts Ir-SpiroPAP, a series of racemic exocyclic γ,δ-unsaturated β-ketoesters bearing a five-, six-, or seven-membered ring were hydrogenated to the corresponding functionalized chiral allylic alcohols in high yields with good to excellent enantioselectivities (87 to >99% ee) and cis-selectivities (93 : 7 to >99 : 1). The origin of the excellent stereoselectivity was also rationalized by density functional theory calculations. Furthermore, this protocol could be performed on gram scale and at a lower catalyst loading (0.002 mol%) without the loss of reactivity and enantioselectivity, and has been successfully applied in the enantioselective synthesis of chiral carbocyclic δ-amino esters and the β-galactosidase inhibitor isogalactofagomine. The Royal Society of Chemistry 2021-04-29 /pmc/articles/PMC8188505/ /pubmed/34168833 http://dx.doi.org/10.1039/d1sc02044g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Bin, Huai-Yu
Cheng, Li
Wu, Xiong
Zhu, Chang-Liang
Yang, Xiao-Hui
Xie, Jian-Hua
Zhou, Qi-Lin
Asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution
title Asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution
title_full Asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution
title_fullStr Asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution
title_full_unstemmed Asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution
title_short Asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution
title_sort asymmetric hydrogenation of exocyclic γ,δ-unsaturated β-ketoesters to functionalized chiral allylic alcohols via dynamic kinetic resolution
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8188505/
https://www.ncbi.nlm.nih.gov/pubmed/34168833
http://dx.doi.org/10.1039/d1sc02044g
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