Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Formation of Hindered Arylcarbamates using Alkyl Aryl Carbonates under Highly Reactive Conditions.

ABSTRACT: Hindered O-tert-alkyl N-arylcarbamates were conveniently prepared by treating arylamines with aryl tert-alkyl carbonates in the presence of a strong base. The new method avoids the use of sensitive and difficult-to-access dialkyl dicarbonates and isocyanates, which are most commonly used in known methods. Instead, the stable and readily accessible alkyl aryl carbonates are used. Therefore, the new method is particularly suitable for the synthesis of N-arylcarbamates that contain a complex O-alkyl moiety. Using the method, electron-rich and electron-poor, and primary and secondary arylamines can all be conveniently converted to their carbamates with acceptable yields. The method was also found equally effective for the synthesis of the less hindered O-secondary and O-primary alkyl N-arylcarbamates.

SUBMITTER: Shahsavari S

PROVIDER: S-EPMC5662102 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Formation of Hindered Arylcarbamates using Alkyl Aryl Carbonates under Highly Reactive Conditions.

Shahsavari Shahien S Gooding James J Wigstrom Travis T Fang Shiyue S

ChemistrySelect 20170510 13

Hindered O-tert-alkyl N-arylcarbamates were conveniently prepared by treating arylamines with aryl tert-alkyl carbonates in the presence of a strong base. The new method avoids the use of sensitive and difficult-to-access dialkyl dicarbonates and isocyanates, which are most commonly used in known methods. Instead, the stable and readily accessible alkyl aryl carbonates are used. Therefore, the new method is particularly suitable for the synthesis of N-arylcarba ...[more]

PMID: 29098174

Similar Datasets

3-D Modelling and Experimental Comparison of Reactive Flow in Carbonates under Radial Flow Conditions.

Project description:We use a two-scale continuum model to simulate reactive flow and wormhole formation in carbonate rocks under 3-D radial flow conditions. More specifically, we present a new structure-property relationship based on the fractal geometry theory, to describe the evolution of local permeability, pore radius, and specific area with porosity variation. In the numerical calculation, to improve the convergence rate, the heterogeneous medium in question is extended by adding a thin layer of homogeneous porous medium to its inlet. We compare the simulation results with the available experimental observations and find that they are qualitatively consistent with each other. Additionally, sensitivity analysis of the dissolution process with respect to acid injection rate and rock heterogeneity, including heterogeneity magnitude and correlation length, is presented.

| S-EPMC5735102 | biostudies-literature

Esterification of Aryl/Alkyl Acids Catalysed by N-bromosuccinimide under Mild Reaction Conditions.

Project description:N-halosuccinimides (NXSs) are well-known to be convenient, easily manipulable and low-priced halogenation reagents in organic synthesis. In the present work, N-bromosuccinimide (NBS) has been promoted as the most efficient and selective catalyst among the NXSs in the reaction of direct esterification of aryl and alkyl carboxylic acids. Comprehensive esterification of substituted benzoic acids, mono-, di- and tri-carboxy alkyl derivatives has been performed under neat reaction conditions. The method is metal-free, air- and moisture-tolerant, allowing for a simple synthetic and isolation procedure as well as the large-scale synthesis of aromatic and alkyl esters with yields up to 100%. Protocol for the recycling of the catalyst has been proposed.

| S-EPMC6225170 | biostudies-literature

Alkyl Aryl Ether Bond Formation with PhenoFluor.

Project description:An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation.

| S-EPMC4487836 | biostudies-literature

Coupling reactions of hindered isonitriles and hindered alkyl thioacids: Mechanistic studies.

Project description:The coupling reaction between hindered thioacids and isonitriles is developed and described. The mechanism for the formation of the thiopyruvamide products is explored, and the method is applied to a selection of substrates.

| S-EPMC2758784 | biostudies-literature

Synthesis of Functionalized Dihydrobenzofurans by Direct Aryl C-O Bond Formation under Mild Conditions.

Project description:A method for the synthesis of dihydrobenzofurans by a direct aryl C-O bond formation is described. A mechanistic pathway for the reaction, distinct from previously described similar transformations, allows for mild reaction conditions that are expected to be compatible with functionalized substrates.

| S-EPMC5189712 | biostudies-literature

Alkyl-(Hetero)Aryl Bond Formation via Decarboxylative Cross-Coupling: A Systematic Analysis.

Project description:Suzuki, Negishi, and Kumada couplings are some of the most important reactions for the formation of skeletal C-C linkages. Their widespread use to forge bonds between two aromatic rings has enabled every branch of chemical science. The analogous union between alkyl halides and metallated aryl systems has not been as widely employed due to the lack of commercially available halide building blocks. Redox-active esters have recently emerged as useful surrogates for alkyl halides in cross-coupling chemistry. Such esters are easily accessible through reactions between ubiquitous carboxylic acids and coupling agents widely used in amide bond formation. This article features an amalgamation of in-house experience bolstered by approximately 200 systematically designed experiments to accelerate the selection of ideal reaction conditions and activating agents for the cross-coupling of primary, secondary, and tertiary alkyl carboxylic acids with both aryl and heteroaryl organometallic species.

| S-EPMC5792188 | biostudies-literature

Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions.

Project description:Cross-coupling reactions between aryl iodide and nucleophiles have been well developed. Iodoniums equipped with a reactive C-I(III) bond accelerate cross-coupling reactions of aryl iodide. Among them, cyclic diaryliodoniums are more atom economical; however; they are often in the trap of metal reliance and encounter regioselectivity issues. Now, we have developed a series of highly reactive cyclic monoaryl-vinyl iodoniums that can be tuned to construct C-N, C-O, and C-C bonds without metal catalysis. Under promotion of triethylamine, coupling reactions with aniline, phenol, aromatic acid, and indole proceed rapidly and regioselectively at room temperature. The carbene species is conceptualized as a key intermediate in our mechanism model. Furthermore, the coupling products enable diversity-oriented synthesis strategy to further build up a chemical library of diverse heterocyclic fragments that are in demand in the drug discovery field. Our current work provides a deep insight into the synthetic application of these highly reactive cyclic iodoniums.

| S-EPMC7338778 | biostudies-literature

Enhanced clickability of doubly sterically-hindered aryl azides.

Project description:Steric character is one of the most fundamental factors to determine the reactivity of the substrate in organic synthesis. In bimolecular reaction, the sterically-bulky group situated close to the reactive center generally prevents the approach of the reaction partner retarding the bond formation. This report describes, to the contrary, significantly enhanced reactivity of 2,6-disubstituted phenyl azides observed in catalyst-free 1,3-dipolar cycloaddition with alkynes, unexpectedly reacting faster than unsubstituted phenyl azide and even more faster than unhindered alkyl azide, despite the steric hindrance adjacent to the reactive azido group. Experimental and computational studies have indicated that the steric hindrance eliciting the inhibition of resonance between azido group and the aromatic ring is the primary cause of this apparently-paradoxical phenomenon. This is the first type of steric acceleration, indicating a possibility of designing a highly reactive functional group by strategically locating it in the sterically-congested environment.

| S-EPMC3216569 | biostudies-literature

Formation of DPM ethers using O-diphenylmethyl trichloroacetimidate under thermal conditions.

Project description:Alcohols are effectively converted to their corresponding diphenylmethyl (DPM) ethers by reaction with O-diphenylmethyl trichloroacetimidate in refluxing toluene without the requirement of a catalyst or other additives. A number of acid and base sensitive substrates were protected in excellent yield using this new method without disturbing the pre-existing functionality present in these molecules. This reaction is the first example of the formation of an ether from stoichiometric amounts of a trichloroacetimidate and an alcohol without the addition of a Brønsted or Lewis acid catalyst.

| S-EPMC4986612 | biostudies-literature

Organocopper cross-coupling reaction for C-C bond formation on highly sterically hindered structures.

Project description:We describe a powerful, broadly applicable cross-coupling protocol that enables carbon-carbon bond formation at highly sterically hindered carbon centers (both sp2 and sp3) by employing organocopper reagents under palladium catalysis. Experimental studies and theoretical calculations indicated that the key to the unique reactivity of copper is the relatively low activation energy of the compact transmetalation transition state, due to Cu(i)-Pd(ii) interaction, which is associated with small values of deformation energy of the reactants. This reaction is applicable to a variety of bulky substrates, including compounds inert to previous cross-coupling chemistry and has high functional group tolerance.

| S-EPMC6585593 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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