Zhao Qingyang, Wen Jialin, Tan Renchang, Huang Kexuan, Metola Pedro, Wang Rui, Anslyn Eric V, Zhang Xumu
Key Laboratory of Preclinical Study for New Drugs of Gansu Province, Lanzhou University, Lanzhou 730000 (China); Department of Chemistry &Chemical Biology, Department of Medicinal Chemistry, Rutgers, The State University of New Jersey, 610 Taylor Road, Piscataway, NJ 08854 (USA).
Angew Chem Int Ed Engl. 2014 Aug 4;53(32):8467-70. doi: 10.1002/anie.201404570. Epub 2014 Jun 18.
Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H 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.
铑/双（膦）-硫脲催化的未保护NH亚胺的不对称氢化反应可提供产率高达97%且对映体过量值（ee）达95%的手性胺。核磁共振氢谱（¹H NMR）研究以及对照实验表明，催化性氯配位中间体通过双重氢键相互作用参与反应机理。氘代实验证明，氢化反应通过与亚胺相符的途径进行。
