Pathways for Arene Oxidation in Non-Heme Diiron Enzymes: Lessons from Computational Studies on Benzoyl Coenzyme A Epoxidase
| Autor: | Tibor András Rokob |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
ONIOM
Models Molecular Benzoyl-coenzyme A Stereochemistry Iron Alkenes 010402 general chemistry Ring (chemistry) 01 natural sciences Biochemistry Catalysis Nonheme Iron Proteins Colloid and Surface Chemistry Coordination Complexes 0103 physical sciences Organic chemistry Computer Simulation chemistry.chemical_classification Olefin fiber 010304 chemical physics Aromaticity General Chemistry 0104 chemical sciences Oxygen Enzyme chemistry Electrophile Epoxy Compounds Acyl Coenzyme A Oxidoreductases Oxidation-Reduction |
| Zdroj: | Journal of the American Chemical Society. 138(44) |
| ISSN: | 1520-5126 |
| Popis: | Oxygenation of aromatic rings using O2 is catalyzed by several non-heme carboxylate-bridged diiron enzymes. In order to provide a general mechanistic description for these reactions, computational studies were carried out at the ONIOM(B3LYP/BP86/Amber) level on the non-heme diiron enzyme benzoyl coenzyme A epoxidase, BoxB. The calculations revealed four possible pathways for attacking the aromatic ring: (a) electrophilic (2e–) attack by a bis(μ-oxo)-diiron(IV) species (Q pathway); (b) electrophilic (2e–) attack via the σ* orbital of a μ-η2:η2-peroxo-diiron(III) intermediate (Pσ* pathway); (c) radical (1e–) attack via the π*-orbital of a superoxo-diiron(II,III) species (Pπ* pathway); (d) radical (1e–) attack of a partially quenched bis(μ-oxo)-diiron(IV) intermediate (Q′ pathway). The results allowed earlier work of de Visser on olefin epoxidation by diiron complexes and QM-cluster studies of Liao and Siegbahn on BoxB to be put into a broader perspective. Parallels with epoxidation using organic peracids we... |
| Databáze: | OpenAIRE |
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