Hydroxylation of aliphatic hydrocarbons with m-chloroperbenzoic acid catalyzed by electron-deficient iron(III) porphyrin complexes

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The catalytic hydroxylation of aliphatic hydrocarbons by m-chloroperbenzoic acid (MCPBA) has been studied in the presence of elecrtron-deficient iron(III) porphyrin complexes. High yields of alcohol products were obtained with small amounts of ketone formation under mild reaction conditions. The stereospecificity and regioselectivity of the iron porphyrin complexes have been investigated in hydroxylation reactions as well. The hydroxylation of alkanes has bran performed in the presence of isotopically O-18-labeled water, (H2O)-O-18, in order to understand the effects of the electronic nature of iron porphyrin complexes, the concentration of H-2 O-18, the C-H bond strength of alkanes, and the reaction temperature on the O-18-incorporation from the labeled water into alcohols. We found that the amounts of O-18 incorporated into the alcohol products varied in the reactions; these results were interpreted with that the reaction of oxygen atom transfer from a high-valent iron oxoporphyrin complex to alkanes competes with that of oxygen atom exchange between the intermediate and labeled water that leads to O-18-incorporation from H-2 O-18 into the alcohol products. Deuterium kinetic isotope effects (KIEs) in the alkane hydroxylations by the iron porphyrin complexes and MCPBA have been studied with a mixture of cyclohexane and cyclohexane-d(12). The KIE values obtained in the reactions were found to depend significantly on the nature to the iron porphyrin complexes. The temperature dependence of k(H)/k(D) was also studied from -40 to 25 degrees C and the parameters of Arrhenius equation (i.e., the pre-exponential factor ratio, A(H)/A(D), and the isotopic difference of C-H and C-D bond activation energies, E-a(D)-E-a(H)) were determined.
Publisher
CHEMICAL SOC JAPAN
Issue Date
1999-04
Language
English
Article Type
Article
Keywords

WATER-SOLUBLE METALLOPORPHYRINS; VALENT IRON-PORPHYRIN; O BOND-CLEAVAGE; ALKANE HYDROXYLATION; MECHANISTIC CRITERION; OXYGEN-TRANSFER; CYTOCHROME-P-450; OXIDATION; EPOXIDATION; PEROXIDASE

Citation

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, v.72, no.4, pp.707 - 713

ISSN
0009-2673
DOI
10.1246/bcsj.72.707
URI
http://hdl.handle.net/10203/240354
Appears in Collection
CH-Journal Papers(저널논문)
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