Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rational Engineering of a Flavoprotein Oxidase for Improved Direct Oxidation of Alcohols to Carboxylic Acids.

ABSTRACT: The oxidation of alcohols to the corresponding carbonyl or carboxyl compounds represents a convenient strategy for the selective introduction of electrophilic carbon centres into carbohydrate-based starting materials. The O?-dependent oxidation of prim-alcohols by flavin-containing alcohol oxidases often yields mixtures of aldehyde and carboxylic acid, which is due to "over-oxidation" of the aldehyde hydrate intermediate. In order to directly convert alcohols into carboxylic acids, rational engineering of 5-(hydroxymethyl)furfural oxidase was performed. In an attempt to improve the binding of the aldehyde hydrate in the active site to boost aldehyde-oxidase activity, two active-site residues were exchanged for hydrogen-bond-donating and -accepting amino acids. Enhanced over-oxidation was demonstrated and Michaelis-Menten kinetics were performed to corroborate these findings.

SUBMITTER: Pickl M

PROVIDER: S-EPMC6149797 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Rational Engineering of a Flavoprotein Oxidase for Improved Direct Oxidation of Alcohols to Carboxylic Acids.

Pickl Mathias M Winkler Christoph K CK Glueck Silvia M SM Fraaije Marco W MW Faber Kurt K

Molecules (Basel, Switzerland) 20171212 12

The oxidation of alcohols to the corresponding carbonyl or carboxyl compounds represents a convenient strategy for the selective introduction of electrophilic carbon centres into carbohydrate-based starting materials. The O₂-dependent oxidation of <i>prim</i>-alcohols by flavin-containing alcohol oxidases often yields mixtures of aldehyde and carboxylic acid, which is due to "over-oxidation" of the aldehyde hydrate intermediate. In order to directly convert alcohols into carboxylic acids, ration ...[more]

PMID: 29231859

Similar Datasets

Production of Hydroxy Acids: Selective Double Oxidation of Diols by Flavoprotein Alcohol Oxidase.

Project description:Flavoprotein oxidases can catalyze oxidations of alcohols and amines by merely using molecular oxygen as the oxidant, making this class of enzymes appealing for biocatalysis. The FAD-containing (FAD=flavin adenine dinucleotide) alcohol oxidase from P. chrysosporium facilitated double and triple oxidations for a range of aliphatic diols. Interestingly, depending on the diol substrate, these reactions result in formation of either lactones or hydroxy acids. For example, diethylene glycol could be selectively and fully converted into 2-(2-hydroxyethoxy)acetic acid. Such a facile cofactor-independent biocatalytic route towards hydroxy acids opens up new avenues for the preparation of polyester building blocks.

| S-EPMC7079103 | biostudies-literature

A Recyclable, Metal-Free Mechanochemical Approach for the Oxidation of Alcohols to Carboxylic Acids.

Project description:The oxidation of primary alcohols under mechanochemical conditions in a Spex8000M Mixer/Mill was investigated. To facilitate ease of separation and recyclability, a polystyrene-bound version of a TEMPO catalyst was employed. When paired with Oxone® in a stainless-steel vial with a stainless-steel ball, several primary alcohols were successfully oxidized to the corresponding carboxylic acids. The product was isolated using gravity filtration, which also allowed for the polystyrene-bound TEMPO catalyst to be recovered and reused in subsequent oxidation reactions. Furthermore, it was demonstrated that the size and steric hindrance of the primary alcohol does not hinder the rate of the reaction. Finally, the aldehyde was selectively obtained from a primary alcohol under ball milling conditions by using a combination of non-supported TEMPO with a copper vial and copper ball.

| S-EPMC7024246 | biostudies-literature

Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization.

Project description:An electrochemical process has been developed for chemoselective oxidation of primary alcohols in lignin to the corresponding carboxylic acids. The electrochemical oxidation reactions proceed under mildly basic conditions and employ 2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO) and 4-acetamido-TEMPO (ACT) as catalytic mediators. Lignin model compounds and related alcohols are used to conduct structure-reactivity studies that provide insights into the origin of the reaction selectivity. The method is applied to the oxidation of lignin extracted from poplar wood chips via a mild acidolysis method, and the reaction affords a novel polyelectrolyte material. Gel permeation chromatography data for the oxidized lignin shows that this material has a molecular weight and molecular weight distribution very similar to that of the extracted lignin, but notable differences are also evident. Base titration reveals a significant increase in the acid content, and the oxidized lignin has much higher water solubility relative to the extracted lignin. Treatment of the oxidized lignin under acidic conditions results in depolymerization of the material into characterized aromatic monomers in nearly 30 wt% yield.

| S-EPMC7641471 | biostudies-literature

Chemoenzymatic Halocyclization of ?,?-Unsaturated Carboxylic Acids and Alcohols.

Project description:A chemoenzymatic method for the halocyclization of unsaturated alcohols and acids by using the robust V-dependent chloroperoxidase from Curvularia inaequalis (CiVCPO) as catalyst has been developed for the in situ generation of hypohalites. A broad range of halolactones and cyclic haloethers are formed with excellent performance of the biocatalyst.

| S-EPMC6973245 | biostudies-literature

A facile method for oxidation of primary alcohols to carboxylic acids and its application in glycosaminoglycan syntheses.

Project description:A convenient two-step, one-pot procedure was developed for the conversion of primary alcohols to carboxylic acids. The alcohol was first treated with NaOCl and TEMPO under phase-transfer conditions, followed by NaClO2 oxidation in one pot. This reaction is applicable to a wide range of alcohols and the mild reaction conditions are compatible with many sensitive functional groups, including electron-rich aromatic rings, acid-labile isopropylidene ketal and glycosidic linkages, and oxidation-prone thioacetal, p-methoxybenzyl, and allyl moieties. Several glycosaminoglycans such as heparin, chondroitin, and hyaluronic acid oligosaccharides have been synthesized in high yields by using this new oxidation protocol.

| S-EPMC1986577 | biostudies-literature

Direct deoxygenative borylation of carboxylic acids.

Project description:Carboxylic acids are readily available, structurally diverse and shelf-stable; therefore, converting them to the isoelectronic boronic acids, which play pivotal roles in different settings, would be highly enabling. In contrast to the well-recognised decarboxylative borylation, the chemical space of carboxylic-to-boronic acid transformation via deoxygenation remains underexplored due to the thermodynamic and kinetic inertness of carboxylic C-O bonds. Herein, we report a deoxygenative borylation reaction of free carboxylic acids or their sodium salts to synthesise alkylboronates under metal-free conditions. Promoted by a uniquely Lewis acidic and strongly reducing diboron reagent, bis(catecholato)diboron (B2cat2), a library of aromatic carboxylic acids are converted to the benzylboronates. By leveraging the same borylative manifold, a facile triboration process with aliphatic carboxylic acids is also realised, diversifying the pool of available 1,1,2-alkyl(trisboronates) that were otherwise difficult to access. Detailed mechanistic studies reveal a stepwise C-O cleavage profile, which could inspire and encourage future endeavours on more appealing reductive functionalisation of oxygenated feedstocks.

| S-EPMC8370987 | biostudies-literature

Photocatalytic direct borylation of carboxylic acids.

Project description:The preparation of high value-added boronic acids from cheap and plentiful carboxylic acids is desirable. To date, the decarboxylative borylation of carboxylic acids is generally realized through the extra step synthesized redox-active ester intermediate or in situ generated carboxylic acid covalent derivatives above 150 °C reaction temperature. Here, we report a direct decarboxylative borylation method of carboxylic acids enabled by visible-light catalysis and that does not require any extra stoichiometric additives or synthesis steps. This operationally simple process produces CO2 and proceeds under mild reaction conditions, in terms of high step economy and good functional group compatibility. A guanidine-based biomimetic active decarboxylative mechanism is proposed and rationalized by mechanistic studies. The methodology reported herein should see broad application extending beyond borylation.

| S-EPMC9675845 | biostudies-literature

DCID-mediated esterification of carboxylic acids with alcohols under mild conditions.

Project description:DCID (Dichloroimidazolidinedione) 2 is used as a novel coupling reagent for the esterification of carboxylic acids with alcohols at room temperature. The reaction represents the first DCID-promoted esterification under mild conditions with good to excellent yields. Reactions can proceed smoothly with those bearing electron-withdrawing and donating group(s) on the carboxylic acids and benzyl alcohols at ambient temperature. Furthermore, we proposed a plausible mechanism and confirmed it by isolating and characterizing intermediates 3a and 7. The structures of the synthesized compounds were confirmed by comparison of melting points and NMR spectra.

| S-EPMC10498154 | biostudies-literature

Reduction of Carboxylic Acids to Alcohols via Manganese(I) Catalyzed Hydrosilylation.

Project description:The reduction of carboxylic acids to the respective alcohols, in mild conditions, was achieved using [MnBr(CO)5] as the catalyst and bench stable PhSiH3 as the reducing agent. It was shown that the reaction with the earth-abundant metal catalyst could be performed either with a catalyst loading as low as 0.5 mol %, rare with the use of [MnBr(CO)5], or on a gram scale employing only 1.5 equiv of PhSiH3, the lowest amount of silane reported to date for this transformation. Kinetic data and control experiments have provided initial insight into the mechanism of the catalytic process, suggesting that it proceeds via the formation of silyl ester intermediates and ligand dissociation to generate a coordinatively unsaturated Mn(I) complex as the active species.

| S-EPMC8395667 | biostudies-literature

KetoABNO/NOx Cocatalytic Aerobic Oxidation of Aldehydes to Carboxylic Acids and Access to α-Chiral Carboxylic Acids via Sequential Asymmetric Hydroformylation/Oxidation.

Project description:A method for aerobic oxidation of aldehydes to carboxylic acids has been developed using organic nitroxyl and NOx cocatalysts. KetoABNO (9-azabicyclo[3.3.1]nonan-3-one N-oxyl) and NaNO2 were identified as the optimal nitroxyl and NOx sources, respectively. The mildness of the reaction conditions enables sequential asymmetric hydroformylation of alkenes/aerobic aldehyde oxidation to access α-chiral carboxylic acids without racemization. The scope, utility, and limitations of the oxidation method are further evaluated with a series of achiral aldehydes bearing diverse functional groups.

| S-EPMC5279997 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data