C1-Symmetric PNP Ligands for Manganese-Catalyzed Enantioselective Hydrogenation of Ketones: Reaction Scope and Enantioinduction Model

被引：55
|
作者：
Zeng, Liyao [1 ,2 ,3 ]
Yang, Huaxin [1 ,2 ]
Zhao, Menglong [1 ,2 ]
Wen, Jialin [1 ,2 ,4 ]
Tucker, James H. R. [3 ]
Zhang, Xumu [1 ,2 ]
机构：
[1] Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
[2] Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
[3] Univ Birmingham, Sch Chem, Birmingham B15 2TT, W Midlands, England
[4] Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, Shenzhen 518055, Peoples R China
来源：
ACS CATALYSIS | 2020年 / 10卷 / 23期
基金：
中国国家自然科学基金;
关键词：
PNP ligand; manganese; asymmetric hydrogenation; ketone; enantioinduction model;
D O I：
10.1021/acscatal.0c04206
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
A family of ferrocene-based chiral PNP ligands is reported. These tridentate ligands were successfully applied in Mn- catalyzed asymmetric hydrogenation of ketones, giving high enantioselectivities (92%similar to 99% ee for aryl alkyl ketones) as well as high efficiencies (TON up to 2000). In additiondialkyl ketones could also be hydrogenated smoothly. Manganese intermediates that might be involved in the catalytic cycle were analyzed. DFT calculation was carried out to help understand the chiral induction model. The Mn/PNP catalyst could discriminate two groups with different steric properties by deformation of the phosphine moiety in the flexible 5-membered ring.
引用
收藏
页码：13794 / 13799
页数：6
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