Browse
Submit Data
Databases
API
Help

Dataset Information

31 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Environmentally Benign, Base-Promoted Selective Amination of Polyhalogenated Pyridines.

ABSTRACT: An environmentally benign, highly efficient, and base-promoted selective amination of various polyhalogenated pyridines including the challenging pyridine chlorides to 2-aminopyridine derivatives using water as solvent has been developed. Featuring the use of the new method, the reaction is extended to the transformation on a large scale. Mechanistic studies indicate that the pathway involving a base aidant dissociation of N,N-dimethylformamide to generate dimethylamine is likely.

SUBMITTER: Sun C

PROVIDER: S-EPMC6648585 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Environmentally Benign, Base-Promoted Selective Amination of Polyhalogenated Pyridines.

Sun Chao C Yao Wubing W Chen Xu X Zhao Yiwen Y Wei Qiqi Q Chen Zishuang Z Wu Jiashou J Hao Feiyue F Xie Huiping H

ACS omega 20190618 6

An environmentally benign, highly efficient, and base-promoted selective amination of various polyhalogenated pyridines including the challenging pyridine chlorides to 2-aminopyridine derivatives using water as solvent has been developed. Featuring the use of the new method, the reaction is extended to the transformation on a large scale. Mechanistic studies indicate that the pathway involving a base aidant dissociation of N,N-dimethylformamide to generate dimethylamine is likely. ...[more]

PMID: 31460151

Similar Datasets

HPW-Catalyzed environmentally benign approach to imidazo[1,2-a]pyridines.

Project description:The imidazo[1,2-a]pyridine moiety is present in drugs with several biological activities. The most direct way of obtaining this nucleus is the Groebke-Blackburn-Bienaymé three-component reaction (GBB-3CR) between aminopyridines, aldehydes, and isocyanides under both Lewis and Brønsted acid catalysis. However, several catalysts for this reaction have major drawbacks such as being expensive, extremely dangerous, strong oxidizing, and even explosive. In this scenario, heteropolyacids emerge as greener and safer alternatives due to their very strong Brønsted acidity. In particular, phosphotungstic acid (HPW) is an economical and green attractive catalyst for being cheap, non-toxic, and is known for its chemical and thermal stability. Herein, we report a straightforward approach to the GBB-3CR using HPW as catalyst in ethanol under microwave (μw) heating. This convenient environmentally benign methodology is broad in scope, provides the heterobicyclic products in high yields (up to 99%), with a low catalyst loading (2 mol %) in only 30 minutes, and allows the successful use of aliphatic aldehydes, substrates not so frequently explored with most usual catalysts for this reaction. Furthermore, the aforementioned advantages make this methodology very attractive and superior to the existing ones.

| S-EPMC10964034 | biostudies-literature

Environmentally Benign Lewis Acid Promoted [2+3]-Dipolar Cycloaddition Reactions of Nitrile Imines with Alkenes in Water.

Project description:Mild and environmentally benign Lewis acid promoted 1,3-dipolar cycloaddition reactions of α-hydrazonyl chlorides with alkenes in water are reported. These α-hydrazonyl chlorides, in the presence of Lewis acids, generate nitrile imines in situ which react with dipolarophiles to furnish the corresponding cycloaddition products. In many cases, the required times for the completion of the Lewis acid promoted 1,3-dipolar cycloaddition reactions in water were comparable to the equivalent reactions performed in an organic solvent. Analogous tetrahexylammonium chloride promoted 1,3-dipolar cycloaddition reactions were also performed. The comparison of reaction times and cycloadduct yields for the aforementioned 1,3-dipolar reactions in aqueous and organic media as well as the proposed role of the Lewis acid in the 1,3-dipolar cycloaddition reaction are described.

| S-EPMC3957226 | biostudies-literature

Ligand-Promoted meta-C-H Amination and Alkynylation.

Project description:Using a modified norbornene (methyl bicyclo[2.2.1]hept-2-ene-2-carboxylate) as a transient mediator, meta-C-H amination and meta-C-H alkynylation of aniline and phenol substrates have been developed for the first time. Both the identification of a monoprotected 3-amino-2-hydroxypyridine/pyridone-type ligand and the use of a modified norbornene as a mediator are crucial for the realization of these two unprecedented meta-C-H transformations. A variety of substrates are compatible with both meta-C-H amination and meta-C-H alkynylation. Amination and alkynylation of heterocyclic substrates including indole, indoline, and indazole afford the desired products in moderate to high yields.

| S-EPMC5513786 | biostudies-literature

Base-Promoted Selective Synthesis of 2H-Pyranones and Tetrahydronaphthalenes via Domino Reactions.

Project description:A highly efficient domino protocol has been developed for the synthesis of 6-aryl-4-(methylthio/amine-1-yl)-2-oxo-2H-pyran-3-carbonitriles and 4-aryl-2-(amine-1-yl)-5,6,7,8-tetrahydronaphthalene-1-carbonitriles from simple and readily available α-aroylketene dithioacetals, malononitrile, secondary amines, and cyclohexanone. This elegant domino process involved consecutive addition-elimination, intramolecular cyclization, and ring opening and closing sequences. Notably, in situ generated 2-imino-4-(methylthio/amine-1-yl)-6-aryl-2H-pyran-3-carbonitrile plays multiple roles in the construction of various novel polyaromatic hydrocarbons.

| S-EPMC6641896 | biostudies-literature

Light-Promoted Electrostatic Adsorption of High-Density Lewis Base Monolayers as Passivating Electron-Selective Contacts.

Project description:Achieving efficient passivating carrier-selective contacts (PCSCs) plays a critical role in high-performance photovoltaic devices. However, it is still challenging to achieve both an efficient carrier selectivity and high-level passivation in a sole interlayer due to the thickness dependence of contact resistivity and passivation quality. Herein, a light-promoted adsorption method is demonstrated to establish high-density Lewis base polyethylenimine (PEI) monolayers as promising PCSCs. The promoted adsorption is attributed to the enhanced electrostatic interaction between PEI and semiconductor induced by the photo-generated carriers. The derived angstrom-scale PEI monolayer is demonstrated to simultaneously provide a low-resistance electrical contact for electrons, a high-level field-effect passivation to semiconductor surface and an enhanced interfacial dipole formation at contact interface. By implementing this light-promoted adsorbed PEI as a single-layered PCSC for n-type silicon solar cell, an efficiency of 19.5% with an open-circuit voltage of 0.641 V and a high fill factor of 80.7% is achieved, which is one of the best results for devices with solution-processed electron-selective contacts. This work not only demonstrates a generic method to develop efficient PCSCs for solar cells but also provides a convenient strategy for the deposition of highly uniform, dense, and ultra-thin coatings for diverse applications.

| S-EPMC7927610 | biostudies-literature

Environmentally benign technology for efficient warm-white light emission.

Project description:Nowadays efficient down conversion for white light emission is mainly based on rare-earth doped phosphors or cadmium-containing quantum dots. Although they exhibit high luminescence efficiency, the rare-earth mining and cadmium pollution have so far led to extremely high environmental cost, which conflicts the original purpose of pursuing efficient lighting. Here, we explore a new strategy to achieve efficient luminescence conversion based on polymer-decorated nanoparticles. The ZnO and Mn(2+) doped ZnS nanoparticles are encapsulated by poly(9,9-di-n- hexylfluorenyl-2,7-diyl). The resultant core-shell nanocomposites then encompass three UV-to-visible luminescence conversion routes for photon emissions at blue, green, and orange colors, respectively. As a result, the color temperature is widely tunable (2100 K ~ 6000 K), so candle light or pure white light can be generated. The quantum yield up to 91% could also be achieved. Such rare-earth-element free nanocomposites give the bright perspectives for energy-saving, healthy, and environmentally benign lighting.

| S-EPMC4058875 | biostudies-other

Selective Halogenation of Pyridines Using Designed Phosphine Reagents.

Project description:Halopyridines are key building blocks for synthesizing pharmaceuticals, agrochemicals, and ligands for metal complexes, but strategies to selectively halogenate pyridine C-H precursors are lacking. We designed a set of heterocyclic phosphines that are installed at the 4-position of pyridines as phosphonium salts and then displaced with halide nucleophiles. A broad range of unactivated pyridines can be halogenated, and the method is viable for late-stage halogenation of complex pharmaceuticals. Computational studies indicate that C-halogen bond formation occurs via an SNAr pathway, and phosphine elimination is the rate-determining step. Steric interactions during C-P bond cleavage account for differences in reactivity between 2- and 3-substituted pyridines.

| S-EPMC7526642 | biostudies-literature

Regioselective Bromine/Magnesium Exchange for the Selective Functionalization of Polyhalogenated Arenes and Heterocycles.

Project description:Using the bimetallic combination sBu2 Mg⋅2 LiOR (R=2-ethylhexyl) in toluene enables efficient and regioselective Br/Mg exchanges with various dibromo-arenes and -heteroarenes under mild reaction conditions and provides bromo-substituted magnesium reagents. Assessing the role of Lewis donor additives in these reactions revealed that N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDTA) finely tunes the regioselectivity of the Br/Mg exchange on dibromo-pyridines and quinolines. Combining spectroscopic with X-ray crystallographic studies, light has been shed on the mixed Li/Mg constitution of the organometallic intermediates accomplishing these transformations. These systems reacted effectively with a broad range of electrophiles, including allyl bromides, ketones, aldehydes, and Weinreb amides in good yields.

| S-EPMC7839478 | biostudies-literature

Palladium-catalysed anti-Markovnikov selective oxidative amination.

Project description:In recent years, the synthesis of amines and other nitrogen-containing motifs has been a major area of research in organic chemistry because they are widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to a reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a palladium-catalysed oxidative amination reaction in which the addition of the nitrogen occurs at the less-substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide through trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favoured products. Both the scope of the transformation and mechanistic investigations are reported.

| S-EPMC6092016 | biostudies-literature

Base-Promoted Radical Azofluoromethylation of Unactivated Alkenes.

Project description:The base-induced reaction of aryl diazonium salts with commercially available CF3SO2Na/CF2HSO2Na allows for the generation of the corresponding diazene radicals along with fluoromethyl radicals. The addition of fluoromethyl radicals to alkenes with subsequent diazene trapping provides the azofluoromethylation products in good to excellent yields. This metal-free method under mild reaction conditions has broad functional group compatibility and is applicable in the late-stage modification of various natural products and bioactive molecules.

| S-EPMC7328341 | 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