Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Green Catalytic Method for Hydrothiolation of Allylamines: An External Electric Field.

ABSTRACT: Based on the idea of environmental friendliness, we first studied the hydrothiolation reactions of thiophenol with allylamine using a green catalyst-an external electric field (EEF). The hydrothiolation reactions could occur through Markovnikov addition (path M) and anti-Markovnikov addition (path AM) pathways. The calculation results demonstrated that when the EEF was oriented along F _-X , F _-Y , and F _+Z directions, path M was accelerated. However, it is favorable for path AM only when the EEF is oriented along the +X and -Y-axes. In addition, the introduction of the EEF further increased and lowered the differences of the reaction barrier as the EEF was oriented along F _-X , F _-Y , and F _+X directions. The solvent effects were also considered in this work. Hopefully, this unprecedented and green catalytic method for the hydrothiolation reactions of allylamine may provide guidance in the lab.

SUBMITTER: Zhang M

PROVIDER: S-EPMC8867569 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Green Catalytic Method for Hydrothiolation of Allylamines: An External Electric Field.

Zhang Mingxia M Li Wenzuo W Zhou Ziyan Z Zhuo Shuping S Su Zhongmin Z

ACS omega 20220211 7

Based on the idea of environmental friendliness, we first studied the hydrothiolation reactions of thiophenol with allylamine using a green catalyst-an external electric field (EEF). The hydrothiolation reactions could occur through Markovnikov addition (path M) and anti-Markovnikov addition (path AM) pathways. The calculation results demonstrated that when the EEF was oriented along F -X , F -Y , and F +Z directions, pat ...[more]

PMID: 35224338

Similar Datasets

External electric field: a new catalytic strategy for the anti-Markovnikov hydrohydrazination of parent hydrazine.

Project description:The anti-Markovnikov hydroamination reaction is considered to be a particular challenge, and one of the reactants, parent hydrazine, is also regarded as a troubling reagent. In this study, we first studied the hydrohydrazination of parent hydrazine via an effective and green catalyst-external electric field (EEF). The calculation results demonstrated that the anti-Markovnikov and Markovnikov pathways are competitive when there was no catalyst. EEF oriented along the negative direction of the X axis (F x ) accelerated the anti-Markovnikov addition reaction. Moreover, it lowered the barrier height of the first step by 16.0 kcal mol-1 (from 27.8 to 11.8 kcal mol-1) when the field strength was 180 (×10-4) au. Under the same conditions, the Markovnikov reaction pathway was inhibited, which means that EEF achieved the specificity of hydrohydrazination. The solvents are favorable for the first step addition reaction, particularly the synergy between solvents and F x lowered the barrier heights by 8.3 (C6H6) and 10.7 (DMSO) kcal mol-1 for an F x = -60 (×10-4) au. Besides, the introduction of the electron-withdrawing substituent (trifluoromethyl) is also a good strategy to catalyze hydrohydrazination, while the electron-donating group (methoxy) is unfavorable.

| S-EPMC8695915 | biostudies-literature

Catalytic Hydrothiolation: Counterion-Controlled Regioselectivity.

Project description:In this Article, we expand upon the catalytic hydrothiolation of 1,3-dienes to afford either allylic or homoallylic sulfides with high regiocontrol. Mechanistic studies support a pathway in which regioselectivity is dictated by the choice of counterion associated with the Rh center. Non-coordinating counterions, such as SbF6-, allow for η4-diene coordination to Rh complexes and result in allylic sulfides. In contrast, coordinating counterions, such as Cl-, favor neutral Rh complexes in which the diene binds η2 to afford homoallylic sulfides. We propose mechanisms that rationalize a fractional dependence on thiol for the 1,2-Markovnikov hydrothiolation while accounting for an inverse dependence on thiol in the 3,4- anti-Markovnikov pathway. Through the hydrothiolation of an essential oil (β-farnesene), we achieve the first enantioselective synthesis of (-)-agelasidine A.

| S-EPMC6563821 | biostudies-literature

Effect of External Electric Field Stress on Gliadin Protein Conformation.

Project description:A molecular dynamic (MD) modeling approach was applied to evaluate the effect of external electric field on gliadin protein structure and surface properties. Static electric field strengths of 0.001 V/nm and 0.002 V/nm induced conformational changes in the protein but had no significant effect on its surface properties. The study of hydrogen bond evolution during the course of simulation revealed that the root mean square deviation, radius of gyration and secondary structure formation, all depend significantly on the number hydrogen bonds formed. This study demonstrated that it is necessary to gain insight into protein dynamics under external electric field stress, in order to develop the novel food processing techniques that can be potentially used to reduce or eradicate food allergens.

| S-EPMC5302742 | biostudies-literature

Directed Self-Assembly of Polarizable Ellipsoids in an External Electric Field.

Project description:The interplay between shape anisotropy and directed long-range interactions enables the self-assembly of complex colloidal structures. As a recent highlight, ellipsoidal particles polarized in an external electric field were observed to associate into well-defined tubular structures. In this study, we systematically investigate such directed self-assembly using Monte Carlo simulations of a two-point-charge model of polarizable prolate ellipsoids. In spite of its simplicity and computational efficiency, we demonstrate that the model is capable of capturing the complex structures observed in experiments on ellipsoidal colloids at low volume fractions. We show that, at sufficiently high electric field strength, the anisotropy in shape and electrostatic interactions causes a transition from three-dimensional crystal structures observed at low aspect ratios to two-dimensional sheets and tubes at higher aspect ratios. Our work thus illustrates the rich self-assembly behavior accessible when exploiting the interplay between competing long- and short-range anisotropic interactions in colloidal systems.

| S-EPMC5719464 | biostudies-literature

General Co-catalytic Hydrothiolation of gem-Difluoroalkenes.

Project description:Regioselective functionalization of gem-difluoroalkenes enables convergent late-stage access to fluorinated functional groups, though most functionalization reactions proceed through defluorinative functionalization processes that deliver mono-fluorovinyl products. In contrast, fewer reactions undergo net hydrofunctionalization to generate difluorinated products. Herein, we report a photocatalytic hydrothiolation of gem-difluoroalkenes that enables access to a broad spectrum of α,α-difluoroalkylthioethers. Notably, the reaction successfully couples nonactivated substrates, which expands the scope of accessible molecules relative to previously reported reactions involving organo- or photocatalytic strategies. Further, this reaction successfully couples biologically relevant molecules under aqueous conditions, highlighting potential applications in both late-stage and biorthogonal functionalizations.

| S-EPMC9772298 | biostudies-literature

What Is the Catalytic Mechanism of Enzymatic Histone N-Methyl Arginine Demethylation and Can It Be Influenced by an External Electric Field?

Project description:Arginine methylation is an important mechanism of epigenetic regulation. Some Fe(II) and 2-oxoglutarate dependent Jumonji-C (JmjC) Nϵ-methyl lysine histone demethylases also have N-methyl arginine demethylase activity. We report combined molecular dynamic (MD) and Quantum Mechanical/Molecular Mechanical (QM/MM) studies on the mechanism of N-methyl arginine demethylation by human KDM4E and compare the results with those reported for N-methyl lysine demethylation by KDM4A. At the KDM4E active site, Glu191, Asn291, and Ser197 form a conserved scaffold that restricts substrate dynamics; substrate binding is also mediated by an out of active site hydrogen-bond between the substrate Ser1 and Tyr178. The calculations imply that in either C-H or N-H potential bond cleaving pathways for hydrogen atom transfer (HAT) during N-methyl arginine demethylation, electron transfer occurs via a σ-channel; the transition state for the N-H pathway is ∼10 kcal/mol higher than for the C-H pathway due to the higher bond dissociation energy of the N-H bond. The results of applying external electric fields (EEFs) reveal EEFs with positive field strengths parallel to the Fe=O bond have a significant barrier-lowering effect on the C-H pathway, by contrast, such EEFs inhibit the N-H activation rate. The overall results imply that KDM4 catalyzed N-methyl arginine demethylation and N-methyl lysine demethylation occur via similar C-H abstraction and rebound mechanisms leading to methyl group hydroxylation, though there are differences in the interactions leading to productive binding of intermediates.

| S-EPMC9212892 | biostudies-literature

Boosting the performance of single-atom catalysts via external electric field polarization.

Project description:Single-atom catalysts represent a unique catalytic system with high atomic utilization and tunable reaction pathway. Despite current successes in their optimization and tailoring through structural and synthetic innovations, there is a lack of dynamic modulation approach for the single-atom catalysis. Inspired by the electrostatic interaction within specific natural enzymes, here we show the performance of model single-atom catalysts anchored on two-dimensional atomic crystals can be systematically and efficiently tuned by oriented external electric fields. Superior electrocatalytic performance have been achieved in single-atom catalysts under electrostatic modulations. Theoretical investigations suggest a universal "onsite electrostatic polarization" mechanism, in which electrostatic fields significantly polarize charge distributions at the single-atom sites and alter the kinetics of the rate determining steps, leading to boosted reaction performances. Such field-induced on-site polarization offers a unique strategy for simulating the catalytic processes in natural enzyme systems with quantitative, precise and dynamic external electric fields.

| S-EPMC9163078 | biostudies-literature

Template-Free Assembly in Living Bacterial Suspension under an External Electric Field.

Project description:Although template-assisted self-assembly methods are very popular in materials and biological systems, they have certain limitations such as lack of tunability and switchable functionality because of the irreversible association of cells and their matrix components. With an aim to achieve more tunability, we have made an attempt to investigate the self-assembly behavior of rod-shaped living bacteria subjected to an external alternating electric field using confocal microscopy. We demonstrate that rod-shaped living bacteria dispersed in a low salinity aqueous medium form different types of reversible freely suspended structures when subjected to an external alternating electric field. At low field strength, an oriented phase is observed where individual bacterium orients with its major axis aligned along the field direction. At intermediate field strength, bacteria align in the form of one-dimensional (1D) chains that lie along the field direction. Further, at high field strength, more bacteria associate with these 1D chains laterally to form a two-dimensional (2D) array. At higher bacterial concentration, these field-induced 2D arrays extend to form three-dimensional columnar structures. These results are discussed in the context of previously reported studies on bacterial self-assembly.

| S-EPMC6044750 | biostudies-literature

Soybean hydrophobic protein response to external electric field: a molecular modeling approach.

Project description:The molecular dynamic (MD) modeling approach was applied to evaluate the effect of an external electric field on soybean hydrophobic protein and surface properties. Nominal electric field strengths of 0.002 V/nm and 0.004 V/nm had no major effect on the structure and surface properties of the protein isolate but the higher electric field strength of 3 V/nm significantly affected the protein conformation and solvent accessible surface area. The response of protein isolate to various external field stresses demonstrated that it is necessary to gain insight into protein dynamics under electromagnetic fields in order to be able to develop the techniques utilizing them for food processing and other biological applications.

| S-EPMC4030879 | biostudies-literature

Catalytic Hydrothiolation: Regio- and Enantioselective Coupling of Thiols and Dienes.

Project description:We report a Rh-catalyzed hydrothiolation of 1,3-dienes, including petroleum feedstocks. Either secondary or tertiary allylic sulfides can be generated from the selective addition of a thiol to the more substituted double bond of a diene. The catalyst tolerates a wide range of functional groups, and the loading can be as low as 0.1 mol %.

| S-EPMC6563822 | 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