248 research outputs found
Oxygen atom transfer using an iron(IV)-oxo embedded in a tetracyclic N-heterocyclic carbene system: How does the reactivity compare to Cytochrome P450 Compound?
Arene activation by a nonheme iron(III)-hydroperoxo complex: Pathways leading to phenol and ketone products:pathways leading to phenol and ketone products
Computational study into the oxidative ring‐closure mechanism during the biosynthesis of deoxypodophyllotoxin
The nonheme iron dioxygenase deoxypodophyllotoxin synthase performs an oxidative ring-closure reaction as part of natural product synthesis in plants. How the enzyme enables the oxidative ring-closure reaction of (-)-yatein and avoids substrate hydroxylation remains unknown. To gain insight into the reaction mechanism and understand the details of the pathways leading to products and byproducts we performed a comprehensive computational study. The work shows that substrate is bound tightly into the substrate binding pocket with the C7’−H bond closest to the iron(IV)-oxo species. The reaction proceeds with hydrogen atom abstraction from the C7’−H position followed by ring-closure and a final hydrogen transfer to form iron(II)-water and deoxypodophyllotoxin. Alternative mechanisms including substrate hydroxylation and an electron transfer pathway were explored but found to be higher in energy. The mechanism is guided by electrostatic perturbations of charged residues in the second-coordination sphere that prevent alternative pathways.<br/
Can Manganese(III)‐Iodosylarene Act as an Oxidant Alongside High‐Valent Manganese(V)‐Oxo Complexes?
Reactivity Differences of Trigonal Pyramidal Nonheme Iron(IV)‐Oxo and Iron(III)‐Oxo Complexes: Experiment and Theory.
Defluorination of fluorophenols by a nonheme iron(IV)‐oxo species: observation of a new intermediate along the reaction
Dramatic rate-enhancement of oxygen atom transfer by an iron(iv)-oxo species by equatorial ligand field perturbations
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