Tags

Type your tag names separated by a space and hit enter

Cobalt-catalyzed highly enantioselective hydrogenation of α,β-unsaturated carboxylic acids.
Nat Commun. 2020 06 26; 11(1):3239.NC

Abstract

Asymmetric hydrogenation of α,β-unsaturated acids catalyzed by noble metals has been well established, whereas, the asymmetric hydrogenation with earth-abundant-metal was rarely reported. Here, we describe a cobalt-catalyzed asymmetric hydrogenation of α,β-unsaturated carboxylic acids. By using chiral cobalt catalyst bearing electron-donating diphosphine ligand, high activity (up to 1860 TON) and excellent enantioselectivity (up to >99% ee) are observed. Furthermore, the cobalt-catalyzed asymmetric hydrogenation is successfully applied to a broad spectrum of α,β-unsaturated carboxylic acids, such as various α-aryl and α-alkyl cinnamic acid derivatives, α-oxy-functionalized α,β-unsaturated acids, α-substituted acrylic acids and heterocyclic α,β-unsaturated acids (30 examples). The synthetic utility of the protocol is highlighted by the synthesis of key intermediates for chiral drugs (6 cases). Preliminary mechanistic studies reveal that the carboxy group may be involved in the control of the reactivity and enantioselectivity through an interaction with the metal centre.

Authors+Show Affiliations

Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China.Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China.Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China.Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China.Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China.Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China.Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China.Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China. chengq@sustech.edu.cn. Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, 518000, Shenzhen, China. chengq@sustech.edu.cn.Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, 518000, Shenzhen, China. zhangxm@sustech.edu.cn.

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

32591536

Citation

Du, Xiaoyong, et al. "Cobalt-catalyzed Highly Enantioselective Hydrogenation of Α,β-unsaturated Carboxylic Acids." Nature Communications, vol. 11, no. 1, 2020, p. 3239.
Du X, Xiao Y, Huang JM, et al. Cobalt-catalyzed highly enantioselective hydrogenation of α,β-unsaturated carboxylic acids. Nat Commun. 2020;11(1):3239.
Du, X., Xiao, Y., Huang, J. M., Zhang, Y., Duan, Y. N., Wang, H., Shi, C., Chen, G. Q., & Zhang, X. (2020). Cobalt-catalyzed highly enantioselective hydrogenation of α,β-unsaturated carboxylic acids. Nature Communications, 11(1), 3239. https://doi.org/10.1038/s41467-020-17057-z
Du X, et al. Cobalt-catalyzed Highly Enantioselective Hydrogenation of Α,β-unsaturated Carboxylic Acids. Nat Commun. 2020 06 26;11(1):3239. PubMed PMID: 32591536.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Cobalt-catalyzed highly enantioselective hydrogenation of α,β-unsaturated carboxylic acids. AU - Du,Xiaoyong, AU - Xiao,Ye, AU - Huang,Jia-Ming, AU - Zhang,Yao, AU - Duan,Ya-Nan, AU - Wang,Heng, AU - Shi,Chuan, AU - Chen,Gen-Qiang, AU - Zhang,Xumu, Y1 - 2020/06/26/ PY - 2020/01/20/received PY - 2020/06/03/accepted PY - 2020/6/28/entrez PY - 2020/6/28/pubmed PY - 2020/6/28/medline SP - 3239 EP - 3239 JF - Nature communications JO - Nat Commun VL - 11 IS - 1 N2 - Asymmetric hydrogenation of α,β-unsaturated acids catalyzed by noble metals has been well established, whereas, the asymmetric hydrogenation with earth-abundant-metal was rarely reported. Here, we describe a cobalt-catalyzed asymmetric hydrogenation of α,β-unsaturated carboxylic acids. By using chiral cobalt catalyst bearing electron-donating diphosphine ligand, high activity (up to 1860 TON) and excellent enantioselectivity (up to >99% ee) are observed. Furthermore, the cobalt-catalyzed asymmetric hydrogenation is successfully applied to a broad spectrum of α,β-unsaturated carboxylic acids, such as various α-aryl and α-alkyl cinnamic acid derivatives, α-oxy-functionalized α,β-unsaturated acids, α-substituted acrylic acids and heterocyclic α,β-unsaturated acids (30 examples). The synthetic utility of the protocol is highlighted by the synthesis of key intermediates for chiral drugs (6 cases). Preliminary mechanistic studies reveal that the carboxy group may be involved in the control of the reactivity and enantioselectivity through an interaction with the metal centre. SN - 2041-1723 UR - https://www.unboundmedicine.com/medline/citation/32591536/Cobalt_catalyzed_highly_enantioselective_hydrogenation_of_αβ_unsaturated_carboxylic_acids_ L2 - http://dx.doi.org/10.1038/s41467-020-17057-z DB - PRIME DP - Unbound Medicine ER -
Try the Free App:
Prime PubMed app for iOS iPhone iPad
Prime PubMed app for Android
Prime PubMed is provided
free to individuals by:
Unbound Medicine.