Substitution effects on the catalytic activity of Mn(III)-porphyrins in epoxidation of alkenes with iodosylbenzene: A comparison between the electron-rich and electron-deficient porphyrins

被引：23
|
作者：
Zakavi, Saeed [1 ]
Ebrahimi, Leila [1 ]
机构：
[1] IASBS, Dept Chem, Zanjan 4513766731, Iran
来源：
POLYHEDRON | 2011年 / 30卷 / 10期
关键词：
Electron-rich and electron-deficient porphyrins; Iodosylbenzene; Mn-porphyrins; Oxidation; Alkenes; MANGANESE PORPHYRINS; HYDROGEN-PEROXIDE; NITROGEN DONORS; PERIODATE; METALLOPORPHYRINS; CONVERSION; COMPLEXES;
D O I：
10.1016/j.poly.2011.04.015
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Oxidation of different olefins with iodosylbenzene in the presence of Mn(III) complexes of meso-tetra(para-tolyl)porphyrin, meso-tetra(ortho-tolyl)porphyrin, meso-tetra(thien-2-yl)porphyrin and beta-hexaboromo-meso-tetra(thien-2-yl)porphyrin as catalyst has been studied. Oxidation of cis- and trans-stilbene in a competitive reaction strongly suggests the involvement of a high valent (porphyrin)Mn=O as the active oxidant intermediate, in the case of each catalyst. Clear observation of the band relevant to a (porphyrin)Mn(IV)=O species in the presence of excess amounts of styrene shows the stability of this moiety towards reaction with olefins. Although, the stability of metalloporphyrins towards oxidative degradation decreases in the order MnT(o-tolyl)P(OAc) > MnT(thien-2-yl)PBr(6)(OAc) > MnT(p-tolyl)-P(OAc) >= MnT(thien-2-yl)P(OAc), a complex pattern of catalytic activity and product (epoxide) selectivity has been found for the Mn-porphyrins in oxidation of various alkenes. (C) 2011 Elsevier Ltd. All rights reserved.
引用
收藏
页码：1732 / 1738
页数：7
相关论文
共 33 条
  • [1] CC BOND FORMATION BETWEEN ELECTRON-RICH AND ELECTRON-DEFICIENT ALKENES
    GIESE, B
    KRETZSCHMAR, G
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1981, 20 (11): : 965 - 966
  • [2] Substitution effects on the UV-vis and 1H NMR spectra of the dications of meso and/or β substituted porphyrins with trifluoroacetic acid: Electron-deficient porphyrins compared to the electron-rich ones
    Zakavi, Saeed
    Omidyan, Reza
    Ebrahimi, Leila
    Heidarizadi, Fatemeh
    INORGANIC CHEMISTRY COMMUNICATIONS, 2011, 14 (11) : 1827 - 1832
  • [3] Comparative study of catalytic activity of some biomimetic models of cytochrome P450 in oxidation of olefins with tetra-n-butylammonium periodate: Electron-rich Mn-porphyrins versus the electron-deficient ones
    Zakavi, Saeed
    Heidarizadi, Fatemeh
    Rayati, Saeed
    INORGANIC CHEMISTRY COMMUNICATIONS, 2011, 14 (06) : 1010 - 1013
  • [4] Gas-phase electrophilic aromatic substitution of electron-rich and electron-deficient aromatic compounds
    Holman, RW
    Eary, T
    Whittle, E
    Gross, ML
    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1998, (10): : 2187 - 2193
  • [5] Crystal engineering for π-π stacking via interaction between electron-rich and electron-deficient heteroaromatics
    Chang, Yu-Chang
    Chen, Yu-Da
    Chen, Chih-Hsin
    Wen, Yuh-Sheng
    Lin, Jiann T.
    Chen, Hsing-Yin
    Kuo, Ming-Yu
    Chao, Ito
    JOURNAL OF ORGANIC CHEMISTRY, 2008, 73 (12): : 4608 - 4614
  • [6] Attractive and repulsive effects in the interactions between electron-rich and electron-deficient groups in peri-substituted naphthalenes
    O'Leary, J
    Bell, PC
    Wallis, JD
    Schweizer, WB
    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 2001, (02): : 133 - 139
  • [7] Evidence for a concerted [4+1]-cycloaddition between electron-rich carbenes and electron-deficient dienes
    Boisvert, Luc
    Beaumier, Francis
    Spino, Claude
    ORGANIC LETTERS, 2007, 9 (26) : 5361 - 5363
  • [8] Cobalt-Catalyzed Hydrogen-Atom Transfer Induces Bicyclizations that Tolerate Electron-Rich and Electron-Deficient Intermediate Alkenes
    Vrubliauskas, Darius
    Vanderwal, Christopher D.
    Vanderwal, Christopher D. (cdv@uci.edu), 1600, John Wiley and Sons Inc (59): : 6171 - 6177
  • [9] Cobalt-Catalyzed Hydrogen-Atom Transfer Induces Bicyclizations that Tolerate Electron-Rich and Electron-Deficient Intermediate Alkenes
    Vrubliauskas, Darius
    Vanderwal, Christopher D.
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2020, 59 (15) : 6115 - 6121
  • [10] Two Types of Cross-Coupling Reactions between Electron-Rich and Electron-Deficient Alkenes Assisted by Nucleophilic Addition Using an Organic Photoredox Catalyst
    Tanaka, Yosuke
    Kubosaki, Suzuka
    Osaka, Kazuyuki
    Yamawaki, Mugen
    Morita, Toshio
    Yoshimi, Yasuharu
    JOURNAL OF ORGANIC CHEMISTRY, 2018, 83 (22): : 13625 - 13635
1234