Cargando…
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...
Autores principales: | , , , , , , |
---|---|
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 |
_version_ | 1783705343220514816 |
---|---|
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. |
format | Online Article Text |
id | pubmed-8188505 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT binhuaiyu asymmetrichydrogenationofexocyclicgdunsaturatedbketoesterstofunctionalizedchiralallylicalcoholsviadynamickineticresolution AT chengli asymmetrichydrogenationofexocyclicgdunsaturatedbketoesterstofunctionalizedchiralallylicalcoholsviadynamickineticresolution AT wuxiong asymmetrichydrogenationofexocyclicgdunsaturatedbketoesterstofunctionalizedchiralallylicalcoholsviadynamickineticresolution AT zhuchangliang asymmetrichydrogenationofexocyclicgdunsaturatedbketoesterstofunctionalizedchiralallylicalcoholsviadynamickineticresolution AT yangxiaohui asymmetrichydrogenationofexocyclicgdunsaturatedbketoesterstofunctionalizedchiralallylicalcoholsviadynamickineticresolution AT xiejianhua asymmetrichydrogenationofexocyclicgdunsaturatedbketoesterstofunctionalizedchiralallylicalcoholsviadynamickineticresolution AT zhouqilin asymmetrichydrogenationofexocyclicgdunsaturatedbketoesterstofunctionalizedchiralallylicalcoholsviadynamickineticresolution |