Sustainable production of dimethyl adipate by non-heme iron(<scp>iii</scp>) catalysed oxidative cleavage of catechol

Jastrzebski, Robin; Berg, Emily J. van den; Weckhuysen, Bert M.; Bruijnincx, Pieter C. A.

doi:10.1039/c4cy01562b

Cited by 14 publications

(12 citation statements)

References 47 publications

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“…Biomimetic models are useful chemical catalysts inspired from Nature. , They are relatively small in size compared to the enzymes that inspired their design and dissolve and react in industrial solvents at room temperature. Several biomimetic model complexes that represent the active site of αKG-dependent halogenases and hydroxylases have been developed previously, including the iron–TPA model (TPA = tris(2-pyridylmethy1)amine), Scheme . This system is well studied and has shown to react with terminal oxidants, such as H 2 O 2 , and reacts with substrates via aliphatic and aromatic hydroxylation and sulfoxidation .…”

Section: Introductionmentioning

confidence: 99%

Group Transfer to an Aliphatic Bond: A Biomimetic Study Inspired by Nonheme Iron Halogenases

et al. 2018

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In this work, we predict a group-transfer reaction to an aliphatic substrate on a biomimetic nonheme iron center based on the structural and functional properties of nonheme iron halogenases. Transferring groups other than halogens to C–H bonds on the same catalytic center would improve the versatility and applicability of nonheme iron halogenases and enhance their use in biotechnology; however, few studies have been reported on this matter. Furthermore, very few biomimetic models are known that are able to transfer halogens or other groups to aliphatic C–H bonds. To gain insight into group transfer to an aliphatic C–H bond, we performed a detailed computational study on a biomimetic nonheme iron complex and studied the reactivity patterns with a model substrate (ethylbenzene). In particular, we investigated the reaction mechanisms of [FeIV(O)(TPA)X]+, TPA = tris(2-pyridylmethy1)amine, and X = Cl, NO2, N3 with ethylbenzene leading to 1-phenylethanol and 1-phenyl-1-X-ethane products. Interestingly, we find that the product distributions vary with the nature of the equatorial X-substituent on the metal center. Thus, [FeIV(O)(TPA)NO2]+ reacts with ethylbenzene by dominant hydroxylation of the substrate, whereas with halide/azide in the cis-position a group transfer is more likely. As such, we predict a catalytic mechanism of azidation of aliphatic groups using a biomimetic nonheme iron oxidant. The results have been analyzed with thermochemical cycles, valence bond schemes and electronic assignments of reactants and products, which put our results in a broad perspective and predict the effect of other substituents. Finally, predictions are given on how these systems could be utilized in vivo.

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Section: Introductionmentioning

confidence: 99%

Group Transfer to an Aliphatic Bond: A Biomimetic Study Inspired by Nonheme Iron Halogenases

et al. 2018

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“…The demethylation of guaiacyl derivatives, for example, leads to catechols, which are present in numerous pharmaceuticals, pesticides, and flavors. Alternatively, catechols are converted by oxidation into muconic acid, which can be hydrogenated to adipic acid derivatives to be used in polymer synthesis …”

Section: Introductionmentioning

confidence: 99%

Exploring the Selective Demethylation of Aryl Methyl Ethers with a Pseudomonas Rieske Monooxygenase

et al. 2018

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Biocatalytic dealkylation of aryl methyl ethers is an attractive reaction for valorization of lignin components, as well as for deprotection of hydroxy functionalities in synthetic chemistry. We explored the demethylation of various aryl methyl ethers by using an oxidative demethylase from Pseudomonas sp. HR199. The Rieske monooxygenase VanA and its partner electron transfer protein VanB were recombinantly coexpressed in Escherichia coli and they constituted at least 25 % of the total protein content. Enzymatic transformations showed that VanB accepts NADH and NADPH as electron donors. The VanA–VanB system demethylates a number of aromatic substrates, the presence of a carboxylic acid moiety is essential, and the catalysis occurs selectively at the meta position to this carboxylic acid in the aromatic ring. The reaction is inhibited by the by‐product formaldehyde. Therefore, we tested three different cascade/tandem reactions for cofactor regeneration and formaldehyde elimination; in particular, conversion was improved by addition of formaldehyde dehydrogenase and formate dehydrogenase. Finally, the biocatalyst was applied for the preparation of protocatechuic acid from vanillic acid, giving a 77 % yield of the desired product. The described reaction may find application in the conversion of lignin components into diverse hydroxyaromatic building blocks and generally offers potential for new, mild methods for efficient unmasking of phenols.

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“…33 Both cis,cis and cis,trans isomers of the muconic acid are observed in the experiments. 34 Although the dioxetane-like species has been discarded based on 18 O 2 labelling studies 35 and theoretical calculations, 36,37 it is still worth analyzing the reactivity of these species because they have been suggested as intermediates for both dioxygenase model systems and for the carotenoid oxygenases. 38,39 The argument that lack of light emission excludes a dioxetane mechanism 40 might not be correct because the O-O bond can be either cleaved with the help of an electron donor, or possibly by the involvement of dark photochemistry.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of the dark photochemistry of 1,3-butadiene via the chemiexcitation of Dewar dioxetane

Farahani

Lundberg

Lindh

et al. 2015

Phys. Chem. Chem. Phys.

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Excited-state chemistry is usually ascribed to photo-induced processes, such as fluorescence, phosphorescence, and photochemistry, or to bio-and chemiluminescence, in which light emission is originated by a chemical reaction. A third class of excited-state chemistry, however, is possible that promotes photochemical phenomena by chemienergizing certain chemical groups without light -chemiexcitation. By studying Dewar dioxetane, which can be viewed as the combination of 1,2-dioxetane and 1,3-butadiene, we show here how the isomerization * To whom correspondence should be addressed † Uppsala ‡ València ¶ UC 3 1 channel that characterizes the photo-induced chemistry of 1,3-butadiene can be reached at a later stage after the thermal decomposition of the dioxetane moiety. Multi-reference multiconfigurational quantum chemistry methods and accurate reaction-path computational strategies were used to determine the reaction coordinate that first decomposes the dioxetane, next transfers non-adiabatically the state from the ground to the excited state, and finally brings the system into the photochemical channel of the 1,3-butadiene group. With the present study, we open a new area of research within computational photochemistry to study chemically-induced excited-state chemistry that is difficult to tackle experimentally due to the short-lived character of the species involved in the process. The findings shall be of relevance to unveil "dark" photochemistry mechanisms which might operate in biological systems in conditions of lack of light to allow reactions that are typical of photo-induced phenomena.

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Sustainable production of dimethyl adipate by non-heme iron(iii) catalysed oxidative cleavage of catechol

Abstract: Selective catechol cleavage by a non-heme iron(iii) complex followed by hydrogenation and transesterifaction yields dimethyl adipate in a green and sustainable manner.

Cited by 14 publications

References 47 publications

Group Transfer to an Aliphatic Bond: A Biomimetic Study Inspired by Nonheme Iron Halogenases

Group Transfer to an Aliphatic Bond: A Biomimetic Study Inspired by Nonheme Iron Halogenases

Exploring the Selective Demethylation of Aryl Methyl Ethers with a Pseudomonas Rieske Monooxygenase

Theoretical study of the dark photochemistry of 1,3-butadiene via the chemiexcitation of Dewar dioxetane

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