ArticleJournal of the American Chemical Society2015
An unusual peroxo intermediate of the arylamine oxygenase of the chloramphenicol biosynthetic pathway.
Article in Journal of the American Chemical Society, 2015. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 39 papers.
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39 citing papers in PubMed, 85 citations in OpenAlex.
- Heme oxygenase-like dimetal oxidases and oxygenases.Biochemical Society transactions · 2026Review
- A two-metalloenzyme cascade constructs the azetidine-containing pharmacophore.Nature chemistry · 2026Article
- The Heme Oxygenase-Like Diiron Enzyme HrmI Reveals Altered Regulatory Mechanisms for Dioxygen Activation and Substrate N-Oxygenation.Journal of the American Chemical Society · 2025Article
- Heme Oxygenase-Like Metalloenzymes.Annual review of biochemistry · 2025Review
- Biochemical Studies of a Cyanobacterial Halogenase Support the Involvement of a Dimetal Cofactor.Biochemistry · 2025Article
- Nature of the Reactive Biferric Peroxy Intermediate P' in the Arylamine Oxygenases and Related Binuclear Fe Enzymes.Journal of the American Chemical Society · 2025Article
- Biocatalytic Strategies for Nitration Reactions.JACS Au · 2025Review
- Heterotrophic nitrification by Alcaligenes faecalis links organic and inorganic nitrogen metabolism.The ISME journal · 2024Article
- Unlocking mild-condition benzene ring contraction using nonheme diironChemical science · 2023Article
- Recent Progress in the Synthesis of Drugs and Bioactive Molecules Incorporating Nitro(het)arene Core.Pharmaceuticals (Basel, Switzerland) · 2022Review
- BesC Initiates C-C Cleavage through a Substrate-Triggered and Reactive Diferric-Peroxo Intermediate.Journal of the American Chemical Society · 2021Article
- Ligand-Constraint-Induced Peroxide Activation for Electrophilic Reactivity.Angewandte Chemie (International ed. in English) · 2021Article
- A nonheme peroxo-diiron(III) complex exhibiting both nucleophilic and electrophilic oxidation of organic substrates.Dalton transactions (Cambridge, England : 2003) · 2021Article
- Structure and assembly of the diiron cofactor in the heme-oxygenase-like domain of theProceedings of the National Academy of Sciences of the United States of America · 2021Article
- In Vitro Reconstitution Reveals a Central Role for the N-Oxygenase PvfB in (Dihydro)pyrazine-N-oxide and Valdiazen Biosynthesis.Angewandte Chemie (International ed. in English) · 2020Article
- A Peroxodiiron(III/III) Intermediate Mediating BothJournal of the American Chemical Society · 2020Article
- Proton-Electron Transfer to the Active Site Is Essential for the Reaction Mechanism of Soluble ΔJournal of the American Chemical Society · 2020Article
- Key Structural Motifs Balance Metal Binding and Oxidative Reactivity in a Heterobimetallic Mn/Fe Protein.Journal of the American Chemical Society · 2020Article
- The Diiron Monooxygenase CmlA from Chloramphenicol Biosynthesis Allows Reconstitution of β-Hydroxylation during Glycopeptide Antibiotic Biosynthesis.ACS chemical biology · 2019Article
- Molecular mechanism of azoxy bond formation for azoxymycins biosynthesis.Nature communications · 2019Article
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Authors and funding
8 authors at 4 institutions in 2 countries.
Funding
Abstract
Streptomyces venezuelae CmlI catalyzes the six-electron oxygenation of the arylamine precursor of chloramphenicol in a nonribosomal peptide synthetase (NRPS)-based pathway to yield the nitroaryl group of the antibiotic. Optical, EPR, and Mössbauer studies show that the enzyme contains a nonheme dinuclear iron cluster. Addition of O(2) to the diferrous state of the cluster results in an exceptionally long-lived intermediate (t(1/2) = 3 h at 4 °C) that is assigned as a peroxodiferric species (CmlI-peroxo) based upon the observation of an (18)O(2)-sensitive resonance Raman (rR) vibration. CmlI-peroxo is spectroscopically distinct from the well characterized and commonly observed cis-μ-1,2-peroxo (μ-η(1):η(1)) intermediates of nonheme diiron enzymes. Specifically, it exhibits a blue-shifted broad absorption band around 500 nm and a rR spectrum with a ν(O-O) that is at least 60 cm(-1) lower in energy. Mössbauer studies of the peroxo state reveal a diferric cluster having iron sites with small quadrupole splittings and distinct isomer shifts (0.54 and 0.62 mm/s). Taken together, the spectroscopic comparisons clearly indicate that CmlI-peroxo does not have a μ-η(1):η(1)-peroxo ligand; we propose that a μ-η(1):η(2)-peroxo ligand accounts for its distinct spectroscopic properties. CmlI-peroxo reacts with a range of arylamine substrates by an apparent second-order process, indicating that CmlI-peroxo is the reactive species of the catalytic cycle. Efficient production of chloramphenicol from the free arylamine precursor suggests that CmlI catalyzes the ultimate step in the biosynthetic pathway and that the precursor is not bound to the NRPS during this step.
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