Biomimetic metal-radical reactivity: aerial oxidation of alcohols, amines, aminophenols and catechols catalyzed by transition metal complexes
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Phalguni Chaudhuri
Abstract
The contributions of the authors to the research program ‘Radicals in Enzymatic Catalysis’ over the last ca. 5 years are summarized. Significant efforts were directed towards the design and testing of phenol-containing ligands for synthesizing radical-containing transition metal complexes as potential candidates for catalysis of organic substrates like alcohols, amines, aminophenols and catechols. Functional models for different copper oxidases, such as galactose oxidase, amine oxidases, phenoxazinone synthase and catechol oxidase, are reported. The copper complexes synthesized can mimic the function of the metalloenzymes galactose oxidase and amine oxidases by catalyzing the aerial oxidation of alcohols and amines. Even methanol could be oxidized, albeit with a low conversion, by a biradical-copper(II) compound. The presence of a primary kinetic isotope effect, similar to that for galactose oxidase, provides compelling evidence that H-atom abstraction from the α-C-atom of the substrates is the rate-limiting step. Although catechol oxidase and phenoxazinone synthase contain copper, manganese(IV) complexes containing radicals have been found to be useful to study synthetic systems and to understand the naturally occurring processes. An ‘on-off’ mechanism of the radicals without redox participation from the metal centers seems to be operative in the catalysis involving such metal-radical complexes.
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©2005 by Walter de Gruyter Berlin New York
Artikel in diesem Heft
- Highlight: Radicals in Enzymatic Catalysis
- Radical-mediated dehydration reactions in anaerobic bacteria
- Heterodisulfide reductase from methanogenic archaea: a new catalytic role for an iron-sulfur cluster
- Structural and functional comparison of HemN to other radical SAM enzymes
- New glycyl radical enzymes catalysing key metabolic steps in anaerobic bacteria
- Unusual reactions involved in anaerobic metabolism of phenolic compounds
- Novel bacterial molybdenum and tungsten enzymes: three-dimensional structure, spectroscopy, and reaction mechanism
- Spectroscopic and theoretical approaches for studying radical reactions in class I ribonucleotide reductase
- Biomimetic metal-radical reactivity: aerial oxidation of alcohols, amines, aminophenols and catechols catalyzed by transition metal complexes
- Combinatorial approaches to functional models for galactose oxidase
- Spectroscopic characterization of the iron-oxo intermediate in cytochrome P450
- Impact of Mycoplasma hyorhinis infection on l-arginine metabolism: differential regulation of the human and murine iNOS gene
- Degradation of the sodium taurocholate cotransporting polypeptide (NTCP) by the ubiquitin-proteasome system
- Identification of three novel mutations in the dihydropyrimidine dehydrogenase gene associated with altered pre-mRNA splicing or protein function
Artikel in diesem Heft
- Highlight: Radicals in Enzymatic Catalysis
- Radical-mediated dehydration reactions in anaerobic bacteria
- Heterodisulfide reductase from methanogenic archaea: a new catalytic role for an iron-sulfur cluster
- Structural and functional comparison of HemN to other radical SAM enzymes
- New glycyl radical enzymes catalysing key metabolic steps in anaerobic bacteria
- Unusual reactions involved in anaerobic metabolism of phenolic compounds
- Novel bacterial molybdenum and tungsten enzymes: three-dimensional structure, spectroscopy, and reaction mechanism
- Spectroscopic and theoretical approaches for studying radical reactions in class I ribonucleotide reductase
- Biomimetic metal-radical reactivity: aerial oxidation of alcohols, amines, aminophenols and catechols catalyzed by transition metal complexes
- Combinatorial approaches to functional models for galactose oxidase
- Spectroscopic characterization of the iron-oxo intermediate in cytochrome P450
- Impact of Mycoplasma hyorhinis infection on l-arginine metabolism: differential regulation of the human and murine iNOS gene
- Degradation of the sodium taurocholate cotransporting polypeptide (NTCP) by the ubiquitin-proteasome system
- Identification of three novel mutations in the dihydropyrimidine dehydrogenase gene associated with altered pre-mRNA splicing or protein function
