Rhodium-Catalyzed Asymmetric Hydrogenation of Unprotected NH Imines Assisted by a Thiourea

被引：115

作者：

Zhao, Qingyang ^{[1
,2
]}

Wen, Jialin ^{[2
]}

Tan, Renchang ^{[2
]}

Huang, Kexuan ^{[2
]}

Metola, Pedro ^{[3
]}

Wang, Rui ^{[1
]}

Anslyn, Eric V. ^{[3
]}

Zhang, Xumu ^{[2
]}

机构：

[1] Key Lab Preclin Study New Drugs Gansu Prov, Lanzhou 730000, Peoples R China

[2] Rutgers State Univ, Dept Chem & Chem Biol, Dept Med Chem, Piscataway, NJ 08854 USA

[3] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 32期

基金：

美国国家科学基金会; 美国国家卫生研究院;

关键词：

asymmetric catalysis; hydrogenation; ion pairs; reaction mechanisms; rhodium; ANION-BINDING CATALYSIS; ENANTIOSELECTIVE TRANSFER HYDROGENATION; REDUCTIVE AMINATION; NONCOVALENT INTERACTIONS; COOPERATIVE CATALYSIS; H IMINES; TRANSITION-METAL; PRIMARY AMINES; COMPLEXES; KETONES;

D O I：

10.1002/anie.201404570

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. H-1 NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine.

引用

页码：8467 / 8470

页数：4

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