Origin of the oxygen atom in C-H bond oxidations catalyzed by a water-soluble metalloporphyrin

被引:38
作者
Balahura, RJ
Sorokin, A
Bernadou, J
Meunier, B
机构
[1] CNRS,CHIM COORDINAT LAB,F-31077 TOULOUSE 4,FRANCE
[2] UNIV GUELPH,DEPT CHEM,GUELPH,ON N1G 2W1,CANADA
关键词
D O I
10.1021/ic9700765
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The monopersulfate oxidation of 4-isopropylbenzoic acid performed in (H2O)-O-18 and catalyzed by a water-soluble metalloporphyrin indicated that half of the oxygen atoms incorporated in 4-(1-hydroxy-1-methylethyl)benzoic acid, the primary hydroxylation product, came from water. A redox tautomerism of the active high-valent hydroxo-metal-oxo porphyrin intermediate coupled with an oxygen rebound mechanism explained this result. Under similar conditions, ketoprofen was directly oxidized to 3-benzoylacetophenone, via at least two different reaction pathways. Trapping of radical intermediates by molecular oxygen competed with the oxygen rebound mechanism.
引用
收藏
页码:3488 / 3492
页数:5
相关论文
共 33 条
[21]   NOVEL METABOLIC PATHWAY OF ARYLETHERS BY CYTOCHROME-P450 - CLEAVAGE OF THE OXYGEN-AROMATIC RING BOND ACCOMPANYING IPSO-SUBSTITUTION BY THE OXYGEN-ATOM OF THE ACTIVE SPECIES IN CYTOCHROME-P450 MODELS AND CYTOCHROME-P450 [J].
OHE, T ;
MASHINO, T ;
HIROBE, M .
ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS, 1994, 310 (02) :402-409
[22]   OXIDATION AT CARBON-1' OF DNA DEOXYRIBOSES BY THE MN-TMPYP/KHSO5 SYSTEM RESULTS FROM A CYTOCHROME P-450-TYPE HYDROXYLATION REACTION [J].
PITIE, M ;
BERNADOU, J ;
MEUNIER, B .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (10) :2935-2936
[23]  
PITIE M, 1992, P NATL ACAD SCI USA, V89, P8967
[24]   EVIDENCE FOR HIGH-VALENT IRON-OXO SPECIES ACTIVE IN THE DNA BREAKS MEDIATED BY IRON-BLEOMYCIN [J].
PRATVIEL, G ;
BERNADOU, J ;
MEUNIER, B .
BIOCHEMICAL PHARMACOLOGY, 1989, 38 (01) :133-140
[25]   STRUCTURE OF MONOMERIC HYDRATED MANGANESE(III) TETRA(4-N-METHYLPYRIDYL)-PORPHYRIN PENTACHLORIDE [J].
PRINCE, S ;
KORBER, F ;
COOKE, PR ;
SMITH, JRL ;
MAZID, MA .
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1993, 49 :1158-1160
[26]   IDENTIFICATION OF THE SOURCE OF OXYGEN IN THE ALKALINE-LABILE PRODUCT ACCOMPANYING CYTOSINE RELEASE DURING BLEOMYCIN-MEDIATED OXIDATIVE-DEGRADATION OF D(CGCGCG) [J].
RABOW, LE ;
MCGALL, GH ;
STUBBE, J ;
KOZARICH, JW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (08) :3203-3208
[27]  
ROBERT A, 1988, NEW J CHEM, V12, P885
[28]   ELECTROSPRAY MASS-SPECTROMETRY OF IRON BLEOMYCIN-II - INVESTIGATION OF THE REACTION OF FE(III) BLEOMYCIN WITH IODOSYLBENZENE [J].
SAM, JW ;
TANG, XJ ;
MAGLIOZZO, RS ;
PEISACH, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (03) :1012-1018
[29]   Metalloporphyrin-catalyzed oxidation of 2-methylnaphthalene to vitamin K-3 and 6-methyl-1,4-naphthoquinone by potassium monopersulfate in aqueous solution [J].
Song, R ;
Sorokin, A ;
Bernadou, J ;
Meunier, B .
JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (03) :673-678
[30]  
Stubbe J, 1996, ACCOUNTS CHEM RES, V29, P322, DOI 10.1021/ar9501333