Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Intermolecular C-O addition of carboxylic acids to arynes.

ABSTRACT: A novel, efficient, and expedient route to biologically and pharmaceutically important o-hydroxyaryl ketones, xanthones, 4-chromanones, and flavones has been developed starting from readily available carboxylic acids and commercially available o-(trimethylsilyl)aryl triflates.

SUBMITTER: Dubrovskiy AV

PROVIDER: S-EPMC2903042 | biostudies-literature | 2010 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Intermolecular C-O addition of carboxylic acids to arynes.

Dubrovskiy Anton V AV Larock Richard C RC

Organic letters 20100701 14

A novel, efficient, and expedient route to biologically and pharmaceutically important o-hydroxyaryl ketones, xanthones, 4-chromanones, and flavones has been developed starting from readily available carboxylic acids and commercially available o-(trimethylsilyl)aryl triflates. ...[more]

PMID: 20545313

Similar Datasets

Intermolecular C-O Addition of Carboxylic Acids to Arynes: Synthesis of o-Hydroxyaryl Ketones, Xanthones, 4-Chromanones, and Flavones.

Project description:An efficient and simple route to biologically and pharmaceutically important o-hydroxyaryl ketones, xanthones, 4-chromanones, and flavones has been developed utilizing readily available carboxylic acids and commercially available o-(trimethylsilyl)aryl triflates.

| S-EPMC3600654 | biostudies-literature

Catalytic enantioselective addition of organometallics to unprotected carboxylic acids.

Project description:Conjugate addition of organometallics to carbonyl based Michael acceptors is a widely used method that allows the building of new carbon-carbon (C-C) bonds and the introduction of chirality in a single step. However, conjugate additions to the simplest Michael acceptors, namely unprotected, unsaturated carboxylic acids, are considered to be prohibited by the fact that acid-base reactions overpower any other type of reactivity, including nucleophilic addition. Here we describe a transient protecting group strategy that allows efficient catalytic asymmetric additions of organomagnesium reagents to unprotected ?,?-unsaturated carboxylic acids. This unorthodox pathway is achieved by preventing the formation of unreactive carboxylate salts by means of a reactive intermediate, allowing modifications of the carbon chain to proceed unhindered, while the stereochemistry is controlled with a chiral copper catalyst. A wide variety of ?-chiral carboxylic acids, obtained with excellent enantioselectivities and yields, can be further transformed into valuable molecules through for instance catalytic decarboxylative cross-coupling reactions.

| S-EPMC6667444 | biostudies-literature

Direct catalytic anti-Markovnikov addition of carboxylic acids to alkenes.

Project description:A direct catalytic anti-Markovnikov addition of carboxylic acids to alkenes is reported. The catalyst system is comprised of the Fukuzumi acridinium photooxidant (1) and a substoichiometric quantity of a hydrogen-atom donor. Oxidizable olefins, such as styrenes, trisubstituted aliphatic alkenes, and enamides, can be employed along with a variety of carboxylic acids to afford the anti-Markovnikov addition adducts exclusively. A deuterium-labeling experiment lends insight to the potential mechanism.

| S-EPMC3757928 | biostudies-literature

Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines.

Project description:This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O-benzoylhydroxylamines as an electrophilic amine source and carboxylic acids as a nucleophilic oxygen source to achieve a modular difunctionalization of olefins. The reaction proceeded in a regioselective manner with moderate to good yields, exhibiting a broad scope of carboxylic acid, amine, and olefin substrates.

| S-EPMC4734347 | biostudies-literature

Intermolecular radical oxyalkylation of arynes with alkenes and TEMPO.

Project description:Radical transformations with arynes represent an underexplored research field and only a few examples have been disclosed. In this research article, the implementation of arynes in three-component reactions with TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and activated alkenes is demonstrated. TEMPO is added to arynes, which triggers a Meerwein-type arylation cascade where the final alkyl radial is eventually trapped by a second equivalent of TEMPO. This method is applicable to activated alkenes such as electron-deficient acrylates, styrenes and also vinyl acetate to provide various bisalkoxyamines. This work is a contribution to the emerging field of radical aryne chemistry.

| S-EPMC11351772 | biostudies-literature

Accelerated microdroplet synthesis of benzimidazoles by nucleophilic addition to protonated carboxylic acids.

Project description:We report a metal-free novel route for the accelerated synthesis of benzimidazole and its derivatives in the ambient atmosphere. The synthetic procedure involves 1,2-aromatic diamines and alkyl or aryl carboxylic acids reacting in electrostatically charged microdroplets generated using a nano-electrospray (nESI) ion source. The reactions are accelerated by orders of magnitude in comparison to the bulk. No other acid, base or catalyst is used. Online analysis of the microdroplet accelerated reaction products is performed by mass spectrometry. We provide evidence for an acid catalyzed reaction mechanism based on identification of the intermediate arylamides. Their dehydration to give benzimidazoles occurs in a subsequent thermally enhanced step. It is suggested that the extraordinary acidity at the droplet surface allows the carboxylic acid to function as a C-centered electrophile. Comparisons of this methodology with data from thin film and bulk synthesis lead to the proposal of three key steps in the reaction: (i) formation of an unusual reagent (protonated carboxylic acid) because of the extraordinary conditions at the droplet interface, (ii) accelerated bimolecular reaction because of limited solvation at the interface and (iii) thermally assisted elimination of water. Eleven examples are shown as evidence of the scope of this chemistry. The accelerated synthesis has been scaled-up to establish the substituent-dependence and to isolate products for NMR characterization.

| S-EPMC8163001 | biostudies-literature

Intermolecular interaction as a direct measure of water solubility advantage of meloxicam cocrystalized with carboxylic acids.

Project description:The solubility advantage (SA) of meloxicam cocrystalized with mono- and dicarboxylic acids was expressed in terms of equilibrium constants involving active pharmaceutical ingredient and coformer in aqueous solutions. It is argued that SA can be quantified by concentration of pairs formed in water. The pH and concentration of dissolved components is included explicitly in the model. The alternative behavior of mono- and dicarboxylic acids was emphasized and addressed to different structural motifs. The structural and energetic properties of meloxicam and its complexes with carboxylic acids were characterized, including tautmerism and dissociation in aqueous media. In particular, performed in silico modeling confirmed experimental observation that meloxicam dissolved in water or modest acidic solutions is expected to be a mixture of anionic form in equilibrium with at least five neutral isomers. Tautomer-related diversity of pairs formation and the possibility of salt formation is also discussed. Graphical abstract Two types of motifs found in meloxicam cocrystals reveal two sources of solubility advantage.

| S-EPMC5911280 | biostudies-literature

Cascade aza-Michael Addition-Cyclizations; Toward Renewable and Multifunctional Carboxylic Acids for Melt-Polycondensation.

Project description:Although the aza-Michael addition reaction on various unsaturated (di-)carboxylic acids and esters of, for example, itaconic acid, is well-known, the consecutive cyclization reaction has not received much attention in literature. The products of this aza-Michael cascade reaction, being mono- or di-carboxylic acid or ester functionalized N-alkyl-pyrrolidone structures, prove interesting for melt-polycondensation reactions as they exhibit excellent stability at elevated temperatures. In other words, this reaction is a toolbox for the generation of renewable monomers and, in turn, polymers with tunable physiological properties. Therefore, this work provides an overview of the state-of-the-art of the cascade aza-Michael addition-cyclization reactions on biobased unsaturated acids and esters, and their use in polymerization reactions. Furthermore, we extend this overview with the cascade aza-Michael addition-cyclization reaction of trans-trimethyl aconitate with di-amines to form a tetra-functional N-alkyl-bis-(pyrrolidone dimethylcarboxylate), which exhibits excellent thermal stability and could effectively be used as monomer in polycondensation reactions. Importantly, the aza-Michael addition reaction between primary amines and trans-trimethyl aconitate can be considered a click-reaction; it proceeds quantitatively within minutes under ambient conditions and follows the principles of green chemistry.

| S-EPMC6868100 | biostudies-literature

Synthesis of Functionalized Cyclopropanes from Carboxylic Acids by a Radical Addition-Polar Cyclization Cascade.

Project description:Herein, we describe the development of a photoredox-catalyzed decarboxylative radical addition-polar cyclization cascade approach to functionalized cyclopropanes. Reductive termination of radical-polar crossover reactions between aliphatic carboxylic acids and electron-deficient alkenes yielded carbanion intermediates that were intercepted in intramolecular alkylations with alkyl chlorides appended to the alkene substrate. The mild conditions, which make use of a readily available organic photocatalyst and visible light, were demonstrated to be amenable to a broad range of structurally complex carboxylic acids and a wide variety of chloroalkyl alkenes, demonstrating exquisite functional group tolerance.

| S-EPMC6282618 | biostudies-literature

Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.

Project description:Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.

| S-EPMC4308744 | 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