EC Number | Metals/Ions | Comment | Organism | Structure |
---|---|---|---|---|
1.14.13.208 | Fe2+ | a non-heme diiron enzyme. The two iron ions are bridged by a glutamate (Glu150). The first Fe2+ is ligated by a glutamate (Glu120) and a histidine (His153), while the second Fe2+ is ligated by an aspartate (Asp211), a glutamate (Glu240) and a histidine (His243) | Aromatoleum evansii |
EC Number | Natural Substrates | Organism | Comment (Nat. Sub.) | Natural Products | Comment (Nat. Pro.) | Rev. | Reac. |
---|---|---|---|---|---|---|---|
1.14.13.208 | benzoyl-CoA + NADPH + H+ + O2 | Aromatoleum evansii | - |
2,3-epoxy-2,3-dihydrobenzoyl-CoA + NADP+ + H2O | - |
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1.14.13.208 | additional information | Aromatoleum evansii | benzoyl-CoA epoxidase is a dinuclear iron enzyme that catalyzes the epoxidation reaction of the aromatic ring of benzoyl-CoA with chemo-, regio- and stereo-selectivity. The enzyme may also catalyze the deoxygenation reaction of epoxide, suggesting a unique bifunctionality among the diiron enzymes | ? | - |
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EC Number | Organism | UniProt | Comment | Textmining |
---|---|---|---|---|
1.14.13.208 | Aromatoleum evansii | Q9AIX7 | - |
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EC Number | Reaction | Comment | Organism | Reaction ID |
---|---|---|---|---|
1.14.13.208 | benzoyl-CoA + NADPH + H+ + O2 = 2,3-epoxy-2,3-dihydrobenzoyl-CoA + NADP+ + H2O | epoxidation starts with the binding of the O2 molecule to the diferrous center to generate a diferric peroxide complex, followed by concerted O-O bond cleavage and epoxide formation. Two different pathways have been located, leading to (2S,3R)-epoxy and (2R,3S)-epoxy products. The barrier difference is 2.8 kcal/mol, corresponding to a diastereomeric excess of about 99:1. Further isomerization from epoxide to phenol has quite a high barrier, which cannot compete with the product release step. After product release into solution, fast epoxide-oxepin isomerization and racemization can take place easily, leading to a racemic mixture of (2S,3R) and (2R,3S) products. The deoxygenation of epoxide to regenerate benzoyl-CoA by a diferrous form of the enzyme proceeds via a stepwise mechanism. The C2-O bond cleavage happens first, coupled with one electron transfer from one iron center to the substrate, to form a radical intermediate, which is followed by the second C3-O bond cleavage. The first step is rate-limiting. Reaction mechanism, modeling and simulations, detailed overview | Aromatoleum evansii |
EC Number | Substrates | Comment Substrates | Organism | Products | Comment (Products) | Rev. | Reac. |
---|---|---|---|---|---|---|---|
1.14.13.208 | benzoyl-CoA + NADPH + H+ + O2 | - |
Aromatoleum evansii | 2,3-epoxy-2,3-dihydrobenzoyl-CoA + NADP+ + H2O | - |
? | |
1.14.13.208 | additional information | benzoyl-CoA epoxidase is a dinuclear iron enzyme that catalyzes the epoxidation reaction of the aromatic ring of benzoyl-CoA with chemo-, regio- and stereo-selectivity. The enzyme may also catalyze the deoxygenation reaction of epoxide, suggesting a unique bifunctionality among the diiron enzymes | Aromatoleum evansii | ? | - |
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EC Number | Synonyms | Comment | Organism |
---|---|---|---|
1.14.13.208 | benzoyl-CoA epoxidase | - |
Aromatoleum evansii |
1.14.13.208 | benzoyl-coenzyme A epoxidase | - |
Aromatoleum evansii |
1.14.13.208 | BoxB | - |
Aromatoleum evansii |
EC Number | Cofactor | Comment | Organism | Structure |
---|---|---|---|---|
1.14.13.208 | NADPH | - |
Aromatoleum evansii |
EC Number | General Information | Comment | Organism |
---|---|---|---|
1.14.13.208 | additional information | benzoyl-CoA substrate forms two hydrogen bonds with Gln116, which in turn is hydrogen-bonded to Glu120. A number of other second-shell residues are also important for the orientation of the benzoyl moiety, including Thr119, Ser123, Phe193, Phe203, and Thr210. Optimized structure of the BoxB active site with the truncated benzoyl-CoA and O2 substrates bound, corresponding to the Michaelis complex, enzyme structure and reaction mechanism mechanics/molecular mechanics calculations and modeling, overview | Aromatoleum evansii |