A Computational Study of Asymmetric Hydrogenation of 2-Phenyl Acrylic Acids Catalyzed by a Rh(I) Catalyst with Ferrocenyl Chiral Bisphosphorus Ligand: The Role of Ion-Pair Interaction†

Fan，Xiangru1; Zheng，Lini1; Yang，Yuhong1; Dong，Xiu Qin2; Zhang，Xumu1; Chung，Lung Wa1

2021-06-01

10.1002/cjoc.202000741

CHINESE JOURNAL OF CHEMISTRY   影响因子和分区

1001-604X

1614-7065

Asymmetric hydrogenation reaction is one of the most efficient synthetic methods to form useful chiral compounds for synthetic chemistry, medicinal chemistry and material chemistry. Generally, the enantioselectivity of many hydrogenation reactions is controlled by steric hindrance between the chiral ligand and substrate. Recently, Zhang group developed a highly asymmetric hydrogenation of 2-aryl and 2-alkyl acrylic acids catalyzed by a Rh(I) catalyst with a chiral Wudaphos ligand. The excellent enantioselectivity of this asymmetric reaction was proposed to be controlled by ion-pair interaction between the substrate and chiral ligand. In this study, a systematic density functional theory study has been carried out to investigate the reaction mechanism and origin of the enantioselectivity. Our computational results suggest that this reaction follows the classic mechanism involving oxidative addition of H, migratory insertion and reductive elimination. Different from the C=C coordination to the metal in the common oxidative addition step, our study found that the chelation of the carboxyl group of the substrate to the cationic Rh(I) metal is more favorable in this oxidative addition step. The high enantioselectivity is proposed to be dictated by a better catalyst/substrate geometric complementarity in the major pathway to have less distortion of the catalyst for a strong ion-pair interaction.

Density functional theory Enantioselectivity Hydrogenation Ion-pair interaction Reaction mechanism

SCI

英语

第一 ; 通讯

WOS:000652594600027

CHEMISTRY

2-s2.0-85106287948

Scopus

1.Department of Chemistry,Guangdong Provincial Key Laboratory of Catalysis and Shenzhen Grubbs Institute,Southern University of Science and Technology,Shenzhen,518055,China
2.Key Laboratory of Biomedical Polymers,Engineering Research Center of Organosilicon Compounds & Materials,Ministry of Education,College of Chemistry and Molecular Sciences,Wuhan University,Wuhan,430072,China

Fan，Xiangru,Zheng，Lini,Yang，Yuhong,等. A Computational Study of Asymmetric Hydrogenation of 2-Phenyl Acrylic Acids Catalyzed by a Rh(I) Catalyst with Ferrocenyl Chiral Bisphosphorus Ligand: The Role of Ion-Pair Interaction†[J]. CHINESE JOURNAL OF CHEMISTRY,2021,39(6):1616-1624.

Fan，Xiangru,Zheng，Lini,Yang，Yuhong,Dong，Xiu Qin,Zhang，Xumu,&Chung，Lung Wa.(2021).A Computational Study of Asymmetric Hydrogenation of 2-Phenyl Acrylic Acids Catalyzed by a Rh(I) Catalyst with Ferrocenyl Chiral Bisphosphorus Ligand: The Role of Ion-Pair Interaction†.CHINESE JOURNAL OF CHEMISTRY,39(6),1616-1624.

Fan，Xiangru,et al."A Computational Study of Asymmetric Hydrogenation of 2-Phenyl Acrylic Acids Catalyzed by a Rh(I) Catalyst with Ferrocenyl Chiral Bisphosphorus Ligand: The Role of Ion-Pair Interaction†".CHINESE JOURNAL OF CHEMISTRY 39.6(2021):1616-1624.