期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 53, 期 7, 页码 1896-1900出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201309515
关键词
hydrogenation; iridium; reaction mechanisms; reactive intermediates; structure elucidation
资金
- Swiss National Science Foundation
Previously elusive iridium dihydride alkene complexes have been identified and characterized by NMR spectroscopy in solution. Reactivity studies demonstrated that these complexes are catalytically competent intermediates. Additional H-2 is required to convert the catalyst-bound alkene into the hydrogenation product, supporting an Ir-III/Ir-V cycle via an [Ir-III(H)(2)(alkene)(H-2)(L)](+) intermediate, as originally proposed based on DFT calculations. NMR analyses indicate a reaction pathway proceeding through rapidly equilibrating isomeric dihydride alkene intermediates with a subsequent slow enantioselectivity-determining step. As in the classical example of asymmetric hydrogenation with rhodium diphosphine catalysts, it is a minor, less stable intermediate that is converted into the major product enantiomer.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据