Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Methanol-Driven Oxidative Rearrangement of Biogenic Furans - Enzyme Cascades vs. Photobiocatalysis.

ABSTRACT: The oxidative ring expansion of bio-derived furfuryl alcohols to densely functionalized six-membered O-heterocycles represents an attractive strategy in the growing network of valorization routes to synthetic building blocks out of the lignocellulosic biorefinery feed. In this study, two scenarios for the biocatalytic Achmatowicz-type rearrangement using methanol as terminal sacrificial reagent have been evaluated, comparing multienzymatic cascade designs with a photo-bio-coupled activation pathway.

SUBMITTER: Jager C

PROVIDER: S-EPMC8058437 | biostudies-literature | 2021

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Methanol-Driven Oxidative Rearrangement of Biogenic Furans - Enzyme Cascades vs. Photobiocatalysis.

Jäger Christina C Bruneau Cloé C Wagner Philip K PK Prechtl Martin H G MHG Deska Jan J

Frontiers in chemistry 20210407

The oxidative ring expansion of bio-derived furfuryl alcohols to densely functionalized six-membered O-heterocycles represents an attractive strategy in the growing network of valorization routes to synthetic building blocks out of the lignocellulosic biorefinery feed. In this study, two scenarios for the biocatalytic Achmatowicz-type rearrangement using methanol as terminal sacrificial reagent have been evaluated, comparing multienzymatic cascade designs with a photo-bio-coupled activation path ...[more]

PMID: 33898389

Similar Datasets

Fully Biocatalytic Rearrangement of Furans to Spirolactones.

Project description:A multienzymatic pathway enables the preparation of optically pure spirolactone building blocks. In a streamlined one-pot reaction cascade, the combination of chloroperoxidase, an oxidase, and an alcohol dehydrogenase renders an efficient reaction cascade for the conversion of hydroxy-functionalized furans to the spirocyclic products. The fully biocatalytic method is successfully employed in the total synthesis of the bioactive natural product (+)-crassalactone D, and as the key module in a chemoenzymatic route yielding lanceolactone A.

| S-EPMC10242749 | biostudies-literature

Intramolecular azavinyl carbene-triggered rearrangement of furans.

Project description:An intramolecular rhodium-catalyzed reaction of 1-tosyl-1,2,3-triazoles with furans has been explored. The tosylimino functionality was found to play a significant chemical role participating in the subsequent domino-transformations of a key reaction intermediate. One of the reaction pathways leads to valuable 2-formyl- and 2-acetylpyridine building blocks, which could be obtained in one-pot starting from easily accessible (furan-2-ylmethyl)propargyl amines. An original method for the synthesis of highly functionalized indolizines from the obtained pyridines has been proposed.

| S-EPMC6839507 | biostudies-literature

Rapid Assembly of Tetrasubstituted Furans via Pummerer-Type Rearrangement.

Project description:Despite the many methods available for the synthesis of furans, few methods remain that allow for the custom-made assembly of fully substituted furans. Here we report a powerful protocol to rapidly construct tetrasubstituted, orthogonally functionalized furans under mild reaction conditions. The developed method involves the regioselective ring-opening of readily available 2,5-dihydrothiophenes followed by an oxidative cyclization to provide the heterocycle. The selective oxidation at sulfur is promoted by N-chlorosuccinimide as an inexpensive reagent and proceeds at ambient temperature in high yield within 30 min. The obtained furans serve as exceptionally versatile intermediates and were shown to participate in a series of valuable postmodifications. The fate of the initial sulfonium intermediate was investigated by mechanistic experiments, and computational studies revealed the existence of an unprecedented Pummerer-type rearrangement. The potential for organic synthesis is highlighted by the total synthesis of bisabolene sesquiterpenoids (pleurotins A, B, and D).

| S-EPMC7884018 | biostudies-literature

A single diiron enzyme catalyses the oxidative rearrangement of tryptophan to indole nitrile.

Project description:Nitriles are uncommon in nature and are typically constructed from oximes through the oxidative decarboxylation of amino acid substrates or from the derivatization of carboxylic acids. Here we report a third nitrile biosynthesis strategy featuring the cyanobacterial nitrile synthase AetD. During the biosynthesis of the eagle-killing neurotoxin, aetokthonotoxin, AetD transforms the 2-aminopropionate portion of 5,7-dibromo-L-tryptophan to a nitrile. Employing a combination of structural, biochemical and biophysical techniques, we characterized AetD as a non-haem diiron enzyme that belongs to the emerging haem-oxygenase-like dimetal oxidase superfamily. High-resolution crystal structures of AetD together with the identification of catalytically relevant products provide mechanistic insights into how AetD affords this unique transformation, which we propose proceeds via an aziridine intermediate. Our work presents a unique template for nitrile biogenesis and portrays a substrate binding and metallocofactor assembly mechanism that may be shared among other haem-oxygenase-like dimetal oxidase enzymes.

| S-EPMC11611611 | biostudies-literature

Borane catalysed ring opening and closing cascades of furans leading to silicon functionalized synthetic intermediates.

Project description:The conversion of renewable biomass resources to synthetically valuable chemicals is highly desirable, but remains a formidable challenge in regards to the substrate scope and reaction conditions. Here we present the development of tris(pentafluorophenyl)borane-catalysed conversion of furans via ring-opening and closing cascade processes to afford silicon-functionalized synthetic chemicals under transition metal-free conditions. The furan ring-opening with hydrosilanes is highly efficient (TON up to 2,000) and atom-economical without forming any byproduct to give rise to α-silyloxy-(Z)-alkenyl silanes. Additional equivalents of silane smoothly induce a subsequent B(C6F5)3-catalysed cyclization of initially formed olefinic silane compounds to produce anti-(2-alkyl)cyclopropyl silanes, another versatile synthon being potentially applicable in the synthesis of natural products and pharmacophores.

| S-EPMC5133710 | biostudies-literature

Biogenic platinum from agricultural wastes extract for improved methanol oxidation reaction in direct methanol fuel cell.

Project description:Platinum is the most commonly used catalyst in fuel cell application. However, platinum is very expensive, thus limits the commercialisation of fuel cell system due to the cost factor. This study introduces a biosynthesis platinum from plant extracts that can reduce the cost of platinum production compared to the conventional method and the hazardous during the production of the catalyst. The biogenic platinum was tested on a Direct Methanol Fuel Cell. Advanced biogenic of Pt nano-cluster was synthesized through a novel and facile of one-pot synthesis bio-reduction derived from natural source in the form of plant extracts as reducing agent. Several selected plant extracts drawn from agricultural waste such as banana peel, pineapple peels and sugarcane bagasse extracts were comparatively evaluated on the ability of phytochemical sources of polyphenols rich for the development of single-step synthesis for Pt NPs. Notably, the biogenic Pt NPs from sugar cane bagasse has superior electro-catalytic activity, the enhanced utilization efficiency of Pt and appreciable stability towards methanol oxidation reaction, whose ECSA value approximates 94.58 m2g-1, mass activity/specific activity (398.20 mAmg-1/0.8471 mA/cm2 Pt) which greater than commercial Pt black (158.12 mAmg-1/1.41 mA/cm2 Pt).

| S-EPMC7753966 | biostudies-literature

Cobalt(III)-catalyzed synthesis of indazoles and furans by C-H bond functionalization/addition/cyclization cascades.

Project description:The development of operationally straightforward and cost-effective routes for the assembly of heterocycles from simple inputs is important for many scientific endeavors, including pharmaceutical, agrochemical, and materials research. In this article we describe the development of a new air-stable cationic Co(III) catalyst for convergent, one-step benchtop syntheses of N-aryl-2H-indazoles and furans by C-H bond additions to aldehydes followed by in situ cyclization and aromatization. Only a substoichiometric amount of AcOH is required as an additive that is both low-cost and convenient to handle. The syntheses of these heterocycles are the first examples of Co(III)-catalyzed additions to aldehydes, and reactions are demonstrated for a variety of aromatic, heteroaromatic, and aliphatic derivatives. The syntheses of both N-aryl-2H-indazoles and furans have been performed on 20 mmol scales and should be readily applicable to larger scales. The reported heterocycle syntheses also demonstrate the use of directing groups that have not previously been applied to Co(III)-catalyzed C-H bond functionalizations. Additionally, the synthesis of furans demonstrates the first example of Co(III)-catalyzed functionalization of alkenyl C-H bonds.

| S-EPMC4304451 | biostudies-literature

Cu(ii)-catalyzed aerobic oxidative coupling of furans with indoles enables expeditious synthesis of indolyl-furans with blue fluorescence.

Project description:With the purpose of incorporating sustainability in chemical processes, there has been a renewed focus on utilizing earth-abundant metal catalysts to expand the repertoire of organic reactions and processes. In this work, we have explored the atom-economic oxidative coupling between two important electron-rich heterocycles - indoles and furans - using commonly available, inexpensive metal catalyst CuCl2·2H2O (<0.25$ per g) to develop an expeditious synthesis of indolyl-furans. Moreover, the reaction proceeded well in the presence of the so-called 'ultimate oxidant' - air, without the need for any external ligand or additive. The reaction was found to be scalable and to work even under partially aqueous conditions. This makes the methodology highly economical, practical, operationally simple and sustainable. In addition, the methodology provides direct access to novel indole-furan-thiophene (IFT)-based electron-rich π-conjugated systems, which show green-yellow fluorescence with large Stokes shift and high quantum yields. Mechanistic investigations reveal that the reaction proceeds through chemoselective oxidation of indole by the metal catalyst followed by the nucleophilic attack by furan.

| S-EPMC10762296 | biostudies-literature

Dissipative biocatalytic cascades and gated transient biocatalytic cascades driven by nucleic acid networks.

Project description:Living systems consist of complex transient cellular networks guiding structural, catalytic, and switchable functions driven by auxiliary triggers, such as chemical or light energy inputs. We introduce two different transient, dissipative, biocatalytic cascades, the coupled glucose oxidase (GOx)/horseradish peroxidase (HRP) glucose-driven oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS2-) to the radical anion (ABTS•-) and the lactate dehydrogenase (LDH)/nicotinamide adenine dinucleotide (NAD+) lactate-driven reduction of NAD+ to NADH. The transient biocatalytic systems are driven by nucleic acid reaction modules using a nucleic acid fuel strand L1' and a nicking enzyme, Nt.BbvCI, as fuel-degrading catalyst, leading to the dynamic spatiotemporal transient formation of structurally proximate biocatalysts activating the biocatalytic cascades and transient coupled processes, including the generation of chemiluminescence and the synthesis of alanine. Subjecting the mixture of biocatalysts to selective inhibitors allows the gated transient operation of the biocatalysts. The kinetics of transient biocatalytic cascades are accompanied by kinetic models and computational simulations.

| S-EPMC9075803 | biostudies-literature

Gold(I)-catalyzed formation of furans by a Claisen-type rearrangement of ynenyl allyl ethers.

Project description:A series of ynenyl allyl ethers were rearranged into polysubstituted furans in the presence of a gold(I) catalyst. It is proposed that the transformation involves a Claisen-type rearrangement that allows the efficient creation of quaternary centers under mild experimental conditions.

| S-EPMC3135071 | 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