Synthesis and catalytic activity of binuclear Mn(III, III)–BINOL complexes for epoxidation of olefins

Patel, Mitesh; Trivedi, Bhavna

doi:10.1002/aoc.1081

Cited by 7 publications

(2 citation statements)

References 21 publications

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“…对于取代的色烯, 催化活性和 ee 值都较理想(表 4, Entries 5～7), 六次回收循环使用催化效能未衰竭 [62] . Trivedi 等 [63] 将联吡啶桥(Bpy) 或菲罗啉 (Phen)…”

Section: 不对称加成催化剂unclassified

Research and Progress in Chiral Binuclear Catalyst of First Row Transition Metal and Corresponding Nonlinear Effect

Yang¹,

Wang²,

Luo³

et al. 2013

Chin. J. Org. Chem.

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The study on chiral binuclear complexes of first row transition metal has been expended to correlated fields such as asymmetric catalysis, biomimetic, functional supramolecular material and medicine, and reaches a research hot point of vast attraction and potential. Contrasting with other traditional organic-metal catalysts, the chiral binuclear complexes which combine several chiral centers and cooperated binuclear often play preferable catalysis behavior in enantioselective reaction. This review covers the recent progress in chiral binuclear complexes of V, Ti, Mn, Fe, Co, Ni, Cu, Zn applied in asymmetric reactions involving asymmetric addition, kinetic resolution, selective oxidation, asymmetric polymerization, as well as the mechanistic investigations. Some studies on the nonlinear effect along with the dimer catalysts are also discussed. The challenges and perspectives are given at the end of this article. Keywords chiral binuclear complexes; first row transition metal; asymmetric catalysis; nonlinear effect 金属有机催化剂种类丰富, 结构复杂多样. 因其具有高催化活性与选择性, 在手性合成中占据着重要地位. 第一过渡系金属元素, 又被称为 3d 金属或轻过渡金属, 它们廉价、环境友好且具备较大的生物相关性 [1] . 与传统单金属催化剂相比, 第一过渡系金属手性双核配合物因催化活性中心增加 [2] 以及双核间的协同作用 [3] , 往往表现出更高的催化活性和较理想的对映选择性 [4] , 特别是对于同时需要双活化的催化反应. 两金属核相互靠近, 也使参与反应的两组分之间结合的熵值降低, 溶剂间重排能垒最小化 [5] . 分子质量的增加也有利于催化剂的分离回收利用 [6] . 吴毓林等 [7] 将双金属催化剂作为催化剂设计领域上的新趋向, 在其专著中予以介绍. 吴毓林等同时还介绍了不对称催化反应中的非线性效应 [7] , 即产物 ee 值与手性助剂或催化剂的 ee 值偏离线性的比例关系 [8] (图 1). Finn 和 Sharpless 等 [9] 认为异手性配体二聚形成高稳定性低催化活性的双核配合物, 消除了催化体系混杂的少量外消旋体, 从而增大了实际参与催化的手性配体的对映纯度. Noyori 等 [10] 也认为同-或异-手性二聚配合物是不对称催化中非线性效应现象的根源. 正的非线性效应又称作手性放大 [11] , 在手性合成应用上有着巨大的发展潜力. 张占金 [12] 和高月华等 [13] 分别介绍了手性双核催化剂在不对称反应中的应用, 但该两篇文献同样都将篇幅集中在了贵重金属铑、铂上. 第一过渡系手性双核配合物在生物酶模拟 [14] , 超分子构建 [15] , 磁光电材料 [16] , 分子识别 [17] 以及手性孔隙多功能材料 [18] 等方面的应用成

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Section: 不对称加成催化剂unclassified

Research and Progress in Chiral Binuclear Catalyst of First Row Transition Metal and Corresponding Nonlinear Effect

Yang¹,

Wang²,

Luo³

et al. 2013

Chin. J. Org. Chem.

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“…According to reusability studies, after the third recycling experiment, even though the performance of the catalysis is 5-7% less than the starting point, it can be re-used as new catalyst in oxidation reactions [36][37][38][39][40][41].…”

Section: Catalytic Investigationmentioning

confidence: 99%

Mild Conditions for Oxidation/Epoxidation of Styrene

Kazanci

Sarıbıyık

Serın

2011

Designed Monomers and Polymers

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In this study, in order to obtain novel support materials for immobilization of transition metals, polymeric Schiff bases were synthesized using a poly-condensation reaction between ortho(o-)phthalaldehyde tere(t-)phthalaldehyde, oxaldehyde and diamines like, e.g., ethylene-p-phenylene-and o-phenylenediamine. Additionally, catalytic activity of polymeric Schiff base metal on oxidation/epoxidation of styrene complexes were investigated. The products have been characterized on the basis of analytical and spectral method, Fourier transform infrared spectroscopy, 1 Hand 13 C-nuclear magnetic resonance, gel-permeation chromatography, elemental analysis, thermogravimetric analysis, atomic adsorbtion spectrometry, gas chromatography and gas chromatography mass spectrometry.

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Effective catalytic oxidation of alcohols and alkenes with monomeric versus dimeric manganese(II) catalysts and t‐BuOOH

Kani

Bolat

2016

Applied Organom Chemis

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= 1,10-phenanthroline; bipy = 2,2′-bipyridine), were synthesized and characterized using UV-visible and infrared spectroscopies and single-crystal X-ray diffraction analyses. Complexes 1 and 2 have six-coordinate octahedral geometry around the Mn(II) centre. Complex 1 is a monomer and consists of a deprotonated monodentate benzoate ligand together with two neutral bidentate amine ligands (phen) and a water molecule. Complex 2 has a dinuclear structure in which two Mn(II) ions share two carboxylate groups, adopting a two-atom bridging mode, and two chelated bipy ligands. Both complexes catalyse the oxidation of alcohols and alkenes in a homogeneous catalytic system consisting of the Mn(II) complex and tert-butyl hydroperoxide (TBHP) in acetonitrile. The system yields good to quantitative conversions of various alkenes and alcohols, such as styrene, ethylbenzene and cyclohexene to their corresponding ketones, and primary alcohols and 1-octanol, 1-heptanol, cyclohexanol, benzyl alcohols and cinnamyl alcohol to their corresponding aldehydes and carboxylic acids. Complexes 1 and 2 exhibit very high activity in the oxidation of cyclohexene to cyclohexanone (ca 80% selectivity) as the main product (ca 94% conversion in 1 h) and of cinnamyl alcohol to cinnamaldehyde (ca 64% selectivity) as the main product (ca 100% conversion in 0.5 h) with TBHP at 70°C in acetonitrile. In addition, optimum reaction conditions were also determined for benzyl alcohol with complexes 1 and 2 and TBHP.

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Synthesis and catalytic activity of binuclear Mn(III, III)–BINOL complexes for epoxidation of olefins

Cited by 7 publications

References 21 publications

Research and Progress in Chiral Binuclear Catalyst of First Row Transition Metal and Corresponding Nonlinear Effect

Research and Progress in Chiral Binuclear Catalyst of First Row Transition Metal and Corresponding Nonlinear Effect

Mild Conditions for Oxidation/Epoxidation of Styrene

Effective catalytic oxidation of alcohols and alkenes with monomeric versus dimeric manganese(II) catalysts and t‐BuOOH

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