Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Resolution of carboxylic acids using copper(I)-promoted removal of propargylic esters under neutral conditions.

ABSTRACT: A method for the optical resolution of carboxylic acids is described. Condensation of racemic carboxylic acids with chiral terminal propargyl alcohols gave separable diastereomeric esters. Chromatographic separation followed by heating the individual diastereomers in methanol with catalytic copper(I) halide regenerated the carboxylic acids in good yields and in enantiomeric ratios of ?94%. This method is particularly useful for the resolution of carboxylic acids that are incompatible with conventional ester hydrolysis.

SUBMITTER: Ghosh P

PROVIDER: S-EPMC3691273 | biostudies-literature | 2011 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Resolution of carboxylic acids using copper(I)-promoted removal of propargylic esters under neutral conditions.

Ghosh Partha P Aubé Jeffrey J

The Journal of organic chemistry 20110414 10

A method for the optical resolution of carboxylic acids is described. Condensation of racemic carboxylic acids with chiral terminal propargyl alcohols gave separable diastereomeric esters. Chromatographic separation followed by heating the individual diastereomers in methanol with catalytic copper(I) halide regenerated the carboxylic acids in good yields and in enantiomeric ratios of ≥94%. This method is particularly useful for the resolution of carboxylic acids that are incompatible with conven ...[more]

PMID: 21491889

Similar Datasets

Copper-Promoted Conjugate Addition of Carboxylic Acids to Ethenesulfonyl Fluoride (ESF) for Constructing Aliphatic Sulfonyl Fluorides.

Project description:A CuO-promoted direct hydrocarboxylation of ethenesulfonyl fluoride (ESF) was developed using carboxylic acid as a nucleophile under mild conditions. A variety of molecules containing both ester group and aliphatic sulfonyl fluoride moiety exhibit great potential in medicinal chemistry and chemical biology. Furthermore, the modification of the known drugs Ibuprofen and Aspirin was also demonstrated.

| S-EPMC8515394 | biostudies-literature

Copper-catalysed enantioselective intramolecular etherification of propargylic esters: synthetic approach to chiral isochromans.

Project description:Enantioselective synthesis of chiral isochromans bearing a terminal alkyne moiety has been accomplished by copper-catalysed enantioselective intramolecular propargylic substitution reactions of propargylic esters with alcoholic nucleophiles. This method represents the first successful example which directly introduced a terminal alkyne group into chiral isochromans.

| S-EPMC9065272 | biostudies-literature

Copper-Catalyzed Decarboxylative Elimination of Carboxylic Acids to Styrenes.

Project description:A copper-catalyzed decarboxylative elimination reaction of (hetero)aromatic propionic acids to vinyl (hetero)arenes has been developed. This method furnishes alkenes from carboxylic acids without the need for stochiometric Pb or Ag additives or expensive or specialized photocatalysts. A series of mechanistic experiments indicate that the reaction proceeds via benzylic deprotonation and subsequent radical decarboxylation; a pathway that is distinct from the single-electron-transfer mechanisms implicated in related decarboxylative elimination reactions.

| S-EPMC10032571 | biostudies-literature

Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(?-cyclodextrin) Copper Complexes.

Project description:It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(?-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1-S3) at neutral pH indicated that the "back-to-back" bisCD complex CuL(1) favoured higher catalytic efficiency and more pronounced enantioselectivity than the "face-to-face" complex CuL(2). The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL(1), which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL(1), even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

| S-EPMC4768151 | biostudies-literature

An improved method for the protection of carboxylic acids as 1,1-dimethylallyl esters.

Project description:1,1-Dimethylallyl (DMA) esters of various N-protected amino acids have been synthesized using prenyldimethylsulfonium tetrafluroborate, a reagent that can be readily made and stored, in conjunction with catalytic CuBr. These reactions were complete within several hours and afforded DMA esters in high yields. As has been previously shown in our group, DMA esters represent a palladium-labile proctecting group for carboxylic acids that resists nucleophilic attack as a tert-butyl ester would.

| S-EPMC2582559 | biostudies-literature

Anaerobic oxidation of aldehydes to carboxylic acids under hydrothermal conditions.

Project description:Examples of anaerobic oxidation of aldehydes in hydrothermal solutions are reported. The reaction using iron(iii) nitrate as the oxidant occurs under mild hydrothermal conditions and generates carboxylic acids in good yields. This method differs from previous studies which use atmospheric oxygen as the oxidant.

| S-EPMC8979077 | biostudies-literature

A convenient, general synthesis of 1,1-dimethylallyl esters as protecting groups for carboxylic acids.

Project description:[reaction: see text] Carboxylic acids were converted in high yield to their 1,1-dimethylallyl (DMA) esters in two steps. Palladium-catalyzed deprotection of DMA esters was shown to be compatible with tert-butyl, benzyl, and Fmoc protecting groups, and Fmoc deprotection could be carried out selectively in the presence of DMA esters. DMA esters were also shown to be resistant to nucleophilic attack, suggesting that they will serve as alternatives to tert-butyl esters when acidic deprotection conditions need to be avoided.

| S-EPMC1482401 | biostudies-literature

Rh(III)-catalyzed decarboxylative coupling of acrylic acids with unsaturated oxime esters: carboxylic acids serve as traceless activators.

Project description:α,β-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with α,β-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermediate, and an isolable rhodium complex sheds further light on the reaction mechanism.

| S-EPMC3985489 | biostudies-literature

Molecular-oxygen-promoted Cu-catalyzed oxidative direct amidation of nonactivated carboxylic acids with azoles.

Project description:A copper-catalyzed oxidative direct formation of amides from nonactivated carboxylic acids and azoles with dioxygen as an activating reagent is reported. The azole amides were produced in good to excellent yields with a broad substrate scope. The mechanistic studies reveal that oxygen plays an essential role in the success of the amidation reactions with copper peroxycarboxylate as the key intermediate. Transamidation occurs smoothly between azole amide and a variety of amines.

| S-EPMC4660991 | 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

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