Catalytic epoxidation and 1,2-dihydroxylation of olefins with bispidine-iron(II)/H2O2 systems

被引：138
作者：
Bukowski, Michael R.
Comba, Peter
Lienke, Achim
Limberg, Christian
de Laorden, Carlos Lopez
Mas-Balleste, Ruben
Merz, Michael
Que, Lawrence, Jr.
机构：
[1] Heidelberg Univ, Anorgan Chem Inst, D-6900 Heidelberg, Germany
[2] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
[3] Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA
[4] Unilever Res Labs, NL-3133 AT Vlaardingen, Netherlands
[5] Humboldt Univ, Inst Chem, D-12489 Berlin, Germany
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2006年 / 45卷 / 21期
关键词：
coordination chemistry; dihydroxylation; epoxidation; homogeneous catalysis; iron;
D O I：
10.1002/anie.200504357
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
(Chemical Equation Presented) Going ferryl: FeII complexes with two isomeric bispidine ligands catalyze the oxidation of cyclooctene with H 2O2 in MeCN under aerobic conditions with high selectivity for the epoxide (see scheme; L = bispidine ligand). An {FeIV=O} complex is postulated to be the oxidant, formed by the homolytic cleavage of the O-O bond of an {FeIII-OOH} intermediate. Performing the reaction under argon gives a mixture of cis and trans diols as well as the epoxide. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.
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收藏
页码：3446 / 3449
页数：4
相关论文
共 37 条
[1]   Spectroscopic characterization of an FeIV intermediate generated by reaction of XO- (X = Cl, Br) with an FeII complex bearing a pentadentate non-porphyrinic ligand -: Hydroxylation and epoxidation activity [J].
Balland, V ;
Charlot, MF ;
Banse, F ;
Girerd, JJ ;
Mattioli, TA ;
Bill, E ;
Bartoli, JF ;
Battioni, P ;
Mansuy, D .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2004, (02) :301-308
[2]   Copper-bispidine coordination chemistry:: Syntheses, structures, solution properties, and oxygenation reactivity [J].
Börzel, H ;
Comba, P ;
Hagen, KS ;
Kerscher, M ;
Pritzkow, H ;
Schatz, M ;
Schindler, S ;
Walter, O .
INORGANIC CHEMISTRY, 2002, 41 (21) :5440-5452
[3]   Iron coordination chemistry with tetra-, penta- and hexadentate bispidine-type ligands [J].
Börzel, H ;
Comba, P ;
Hagen, KS ;
Lampeka, YD ;
Lienke, A ;
Linti, G ;
Merz, M ;
Pritzkow, H ;
Tsymbal, LV .
INORGANICA CHIMICA ACTA, 2002, 337 :407-419
[4]  
Buda F, 2001, CHEM-EUR J, V7, P2775, DOI 10.1002/1521-3765(20010702)7:13<2775::AID-CHEM2775>3.0.CO
[5]  
2-6
[6]  
Bukowski M. R., 2004, ANGEW CHEM, V116, P1303
[7]   Bispidine ligand effects on iron/hydrogen peroxide chemistry [J].
Bukowski, MR ;
Comba, P ;
Limberg, C ;
Merz, M ;
Que, L ;
Wistuba, T .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (10) :1283-1287
[8]  
Burger RM, 2000, STRUCT BOND, V97, P287
[9]   Spin state tuning of non-heme iron-catalyzed hydrocarbon oxidations:: participation of FeIII-OOH and FeV=O intermediates [J].
Chen, K ;
Costas, M ;
Que, L .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (05) :672-679
[10]   Tuning the properties of copper(II) complexes with tetra- and pentadentate bispidine (=3,7-diazabicyclo[3.3.1]nonane) ligands [J].
Comba, P ;
de Laorden, CL ;
Pritzkow, H .
HELVETICA CHIMICA ACTA, 2005, 88 (03) :647-664
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