Origin of the minor enantiomeric product in a noyori asymmetric hydrogenation: Evidence for pathways different to the major mechanism

被引:10
作者
Ishibashi, Y
Bessho, Y
Yoshimura, M
Tsukamoto, M
Kitamura, M [1 ]
机构
[1] Nagoya Univ, Res Ctr Mat Sci, Chikusa Ku, Nagoya, Aichi 4648602, Japan
[2] Nagoya Univ, Dept Chem, Chikusa Ku, Nagoya, Aichi 4648602, Japan
关键词
enantioselectivity; homogeneous catalysis; hydrogenation; isotopic labeling; reaction mechanisms;
D O I
10.1002/anie.200502463
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
(Chemical Equation Presented) Hidden pathways: The enantiomeric products of the catalytic hydrogenation of an isotopically labeled substrate were separated. The ratios of the isotopomers revealed that the major and minor enantiomers are formed mostly through different mechanisms. Hence, when analyzing the energy profile of an asymmetric catalytic reaction with the Arrhenius equation, two competing diastereomorphic catalytic cycles should be considered (see scheme). © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码:7287 / 7290
页数:4
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