Ruthenium-catalyzed asymmetric epoxidation of olefins using H2O2, Part II:: Catalytic activities and mechanism

被引:80
作者
Tse, MK
Bhor, S
Klawonn, M
Anilkumar, G
Jiao, HJ
Spannenberg, A
Döbler, C
Mägerlein, W
Hugl, H
Beller, M
机构
[1] Univ Rostock, Leibniz Inst Organ Katalyse, D-18059 Rostock, Germany
[2] LANXESS Deutschland GmbH, BU Fine Chem, D-51369 Leverkusen, Germany
关键词
asymmetric oxidation; epoxidation; homogeneous catalysis; mechanism; olefins; ruthenium;
D O I
10.1002/chem.200501262
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Asymmetric epoxidation of olefins with 30% H2O2 in the presence of [Ru(pybox)(pydic)] 1 and [Ru(pyboxazine)(pydic)] 2 has been studied in detail (pybox=pyridine-2,6-bisoxazoline, pyboxazine=pyridine2,6-bisoxazine, pydic=2,6-pyridinedi-carboxylate). 35 Ruthenium complexes with sterically and electronically different substituents have been tested in environmentally benign epoxidation reactions. Mono-, 1,1-di-, cis- and trans-1,2- di-, tri-, and tetra-substituted aromatic olefins with versatile functional groups can be epoxidized with this type of catalyst in good to excellent yields (up to 100%) with moderate to good enantio-selectivies (up to 84% ee). Additive and solvent effects as well as the relative rate of reaction with different catalysts have been established. It is shown that the presence of weak organic acids or an electron-withdrawing group on the catalyst increases the reactivity. New insights on the reaction intermediates and reaction pathway of the ruthenium-catalyzed epoxidation are proposed on the basis of density functional theory calculation and experiments.
引用
收藏
页码:1875 / 1888
页数:14
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