ArticleJournal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry2018
On how the binding cavity of AsqJ dioxygenase controls the desaturation reaction regioselectivity: a QM/MM study.
Article in Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry, 2018. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 12 papers.
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12 citing papers in PubMed.
- Mechanistic insights into the selective oxidation of D-arginine by the nonheme iron-dependent viomycin biosynthesis enzyme VioC.iScience · 2025Article
- Substrate Epoxidation Catalyzed by the Nonheme Iron Dioxygenase Dapdiamide Biosynthesis Enzyme C. Why Is the Substrate Tethered?Chemistry (Weinheim an der Bergstrasse, Germany) · 2025Article
- The Unique Role of the Second Coordination Sphere to Unlock and Control Catalysis in Nonheme Fe(II)/2-Oxoglutarate Histone Demethylase KDM2A.Inorganic chemistry · 2024Article
- Revealing the Catalytic Strategy of FTO.Chem catalysis · 2023Article
- Elucidation of divergent desaturation pathways in the formation of vinyl isonitrile and isocyanoacrylate.Nature communications · 2022Article
- Harnessing the Substrate Promiscuity of Dioxygenase AsqJ and Developing Efficient Chemoenzymatic Synthesis for Quinolones.ACS catalysis · 2021Article
- Fungal Dioxygenase AsqJ Is Promiscuous and Bimodal: Substrate-Directed Formation of Quinolones versus Quinazolinones.Angewandte Chemie (International ed. in English) · 2021Article
- Regioselectivity of hyoscyamine 6β-hydroxylase-catalysed hydroxylation as revealed by high-resolution structural information and QM/MM calculations.Dalton transactions (Cambridge, England : 2003) · 2020Article
- Mechanistic Insights into a Stibene Cleavage Oxygenase NOV1 from Quantum Mechanical/Molecular Mechanical Calculations.ChemistryOpen · 2019Article
- Advances in Sustainable Catalysis: A Computational Perspective.Frontiers in chemistry · 2019Review
- Mechanisms of Cytochrome P450-Catalyzed Oxidations.ACS catalysis · 2018Article
- Computational Understanding of the Selectivities in Metalloenzymes.Frontiers in chemistry · 2018Review
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Abstract
The Fe(II)/2-oxoglutarate-dependent dioxygenase AsqJ from Aspergillus nidulans catalyses two pivotal steps in the synthesis of quinolone antibiotic 4'-methoxyviridicatin, i.e., desaturation and epoxidation of a benzodiazepinedione. The previous experimental results signal that, during the desaturation reaction, hydrogen atom transfer (HAT) from the benzylic carbon atom (C10) is a more likely step to initiate the reaction than the alternative HAT from the ring moiety (C3 atom). To unravel the origins of this regioselectivity and to explain why the observed reaction is desaturation and not the "default" hydroxylation, we performed a QM/MM study on the reaction catalysed by AsqJ. Herein, we report results that complement the experimental findings and suggest that HAT at the C10 position is the preferred reaction due to favourable interactions between the substrate and the binding cavity that compensate for the relatively high intrinsic barrier associated with the process. For the resultant radical intermediate, the desaturation/hydroxylation selectivity is governed by electronic properties of the reactants, i.e., the energy gap between the orbital that hosts the unpaired electron and the sigma orbital for the C-H bond as well as the gap between the orbitals mixing in transition state structures for each elementary step. Regiospecificity of the AsqJ dehydrogenation reaction is dictated by substrate-protein interactions. 82 × 44 mm (300 × 300 dpi).
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