Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Highly Efficient Gold(I)-Catalyzed Regio- and Stereoselective Hydrocarboxylation of Internal Alkynes.

ABSTRACT: We report the highly efficient gold-catalyzed hydrocarboxylation of internal alkynes that operates under solvent- and silver-free conditions. This new, simple, and eco-friendly protocol allows for the synthesis of a wide variety of functionalized aryl and alkyl enol esters in high yields, with Z-stereospecificity and good regioselectivities and without the requirement for purification by chromatography. This process represents an expedient, operationally simple method for the synthesis of enol esters.

SUBMITTER: Dupuy S

PROVIDER: S-EPMC5745071 | biostudies-literature | 2015 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Highly Efficient Gold(I)-Catalyzed Regio- and Stereoselective Hydrocarboxylation of Internal Alkynes.

Dupuy Stéphanie S Gasperini Danila D Nolan Steven P SP

ACS catalysis 20151012 11

We report the highly efficient gold-catalyzed hydrocarboxylation of internal alkynes that operates under solvent- and silver-free conditions. This new, simple, and eco-friendly protocol allows for the synthesis of a wide variety of functionalized aryl and alkyl enol esters in high yields, with <i>Z</i>-stereospecificity and good regioselectivities and without the requirement for purification by chromatography. This process represents an expedient, operationally simple method for the synthesis of ...[more]

PMID: 29291135

Similar Datasets

Hydroxy group-enabled highly regio- and stereo-selective hydrocarboxylation of alkynes.

Project description:Here we present an example of utilizing hydroxy groups for regioselectivity control in the addition reaction of alkynes-a highly efficient Pd-catalyzed syn-hydrocarboxylation of readily available 2-alkynylic alcohols with CO in the presence of alcohols with an unprecedented regioselectivity affording 3-hydroxy-2(E)-alkenoates. The role of the hydroxy group has been carefully studied. The synthetic potential of the products has also been demonstrated.

| S-EPMC6544123 | biostudies-literature

Stereoselective Gold(I)-Catalyzed Intermolecular Hydroalkoxlation of Alkynes.

Project description:We report the use of cationic gold complexes [Au(NHC)(CH3CN)][BF4] and [{Au(NHC)}2(?-OH)][BF4] (NHC = N-heterocyclic carbene) as highly active catalysts in the solvent-free hydroalkoxylation of internal alkynes using primary and secondary alcohols. Using this simple protocol, a broad range of (Z)-vinyl ethers were obtained in excellent yields and high stereoselectivities. The methodology allows for the use of catalyst loadings as low as 200 ppm for the addition of primary alcohols to internal alkynes (TON = 35 000, TOF = 2188 h-1).

| S-EPMC5745073 | biostudies-literature

Highly regio- and stereoselective phosphinylphosphination of terminal alkynes with tetraphenyldiphosphine monoxide under radical conditions.

Project description:The homolytic cleavage of the PV(O)-PIII bond in tetraphenyldiphosphine monoxide simultaneously provides both pentavalent and trivalent phosphorus-centered radicals with different reactivities. The method using V-40 as an initiator is successfully investigated for the regio- and stereoselective phosphinylphosphination of terminal alkynes giving the corresponding trans-isomers of 1-diphenylphosphinyl-2-diphenylthiophosphinyl-1-alkenes in good yields. The protocol can be applied to a wide variety of terminal alkynes including both alkyl- and arylalkynes.

| S-EPMC8077611 | biostudies-literature

Highly Efficient and Stereoselective Thioallylation of Alkynes: Possible Gold Redox Catalysis with No Need for a Strong Oxidant.

Project description:Stereoselective thioallylation of alkynes under possible gold redox catalysis was accomplished with high efficiency (as low as 0.1?% catalyst loading, up to 99?% yield) and broad substrate scope (various alkynes, inter- and intramolecular fashion). The gold(I) catalyst acts as both a ?-acid for alkyne activation and a redox catalyst for AuI/III coupling, whereas the sulfonium cation generated in situ functions as a mild oxidant. This novel methodology provides an exciting system for gold redox catalysis without the need for a strong oxidant.

| S-EPMC6121218 | biostudies-literature

Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes.

Project description:A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers.

| S-EPMC3817533 | biostudies-literature

Regio- and stereoselective access to highly substituted vinylphosphine oxides via metal-free electrophilic phosphonoiodination of alkynes.

Project description:In general, the P-centered ring-opening of quaternary phosphirenium salts (QPrS) predominantly leads to hydrophosphorylated products, while the C-centered ring-opening is primarily confined to intramolecular nucleophilic reactions, resulting in the formation of phosphorus-containing cyclization products instead of difunctionalized products generated through intermolecular nucleophilic processes. Here, through the promotion of ring-opening of three-member rings by iodine anions and the quenching of electronegative carbon atoms by iodine cations, we successfully synthesize β-functionalized vinylphosphine oxides by the P-addition of QPrS intermediates generated in situ. Multiple β-iodo-substituted vinylphosphine oxides can be obtained with exceptional regio- and stereo-selectivity by reacting secondary phosphine oxides with unactivated alkynes. In addition, a variety of β-functionalized vinylphosphine oxides converted from C-I bonds, especially the rapid construction of benzo[b]phospholes oxides, demonstrates the significance of this strategy.

| S-EPMC11199708 | biostudies-literature

Silver-Catalyzed Stereoselective Aminosulfonylation of Alkynes.

Project description:A silver-catalyzed intermolecular aminosulfonylation of terminal alkynes with sodium sulfinates and TMSN3 is reported. This three-component reaction proceeds through sequential hydroazidation of the terminal alkyne and addition of a sulfonyl radical to the resultant vinyl azide. The method enables the stereoselective synthesis of a wide range of ?-sulfonyl enamines without electron-withdrawing groups on the nitrogen atom. These enamines are found to be suitable for a variety of further transformations.

| S-EPMC5655761 | biostudies-literature

Stereoselective cobalt-catalyzed halofluoroalkylation of alkynes.

Project description:Stereoselective additions of highly functionalized reagents to available unsaturated hydrocarbons are an attractive synthetic tool due to their high atom economy, modularity, and rapid generation of complexity. We report efficient cobalt-catalyzed (E)-halofluoroalkylations of alkynes/alkenes that enable the construction of densely functionalized, stereodefined fluorinated hydrocarbons. The mild conditions (2 mol% cat., 20 °C, acetone/water, 3 h) tolerate various functional groups, i.e. halides, alcohols, aldehydes, nitriles, esters, and heteroarenes. This reaction is the first example of a highly stereoselective cobalt-catalyzed halo-fluoroalkylation. Unlike related cobalt-catalyzed reductive couplings and Heck-type reactions, it operates via a radical chain mechanism involving terminal halogen atom transfer which obviates the need for a stoichiometric sacrificial reductant.

| S-EPMC5892352 | biostudies-literature

Gold-Catalyzed Hydrofluorination of Electron-Deficient Alkynes: Stereoselective Synthesis of <i>β</i>-Fluoro Michael Acceptors.

Project description:The gold(I)-catalyzed, stereoselective hydrofluorination of electron-deficient alkynes with triethylamine trihydrogen fluoride (Et3N·3HF) is described. Fluorinated α,β-unsaturated aldehydes, amides, esters, ketones, and nitriles were isolated in moderate to good yields as single diastereomers. In all but four cases, the (Z)-vinyl fluorides were initially formed in ≥97% diastereoselectivity. This work constitutes the first catalytic example of the diastereoselective preparation of a variety of β-alkyl, β-fluoro Michael acceptors from alkynes. Additionally, the described work expands access to β-aryl, β-fluoro Michael acceptors to the synthesis of β-fluoro-α,β-unsaturated amides and nitriles. The monofluoroalkenes formed through this strategy were readily transformed into other fluorine-containing compounds, and the developed method was applied to the synthesis of a fluorinated analogue of Exoderil, a topical antimycotic.

| S-EPMC6874379 | biostudies-literature

Regio- and Stereoselective Radical Perfluoroalkyltriflation of Alkynes Using Phenyl(perfluoroalkyl)iodonium Triflates.

Project description:A method for regio- and stereoselective anti-addition of the perfluoroalkyl and the triflate group of phenyl(perfluoroalkyl)iodonium triflates to alkynes is presented. The radical reaction uses cheap CuCl as a smart initiator and can be conducted in gram scale. The perfluoroalkyltriflated products are readily further functionalized, rendering this transformation valuable.

| S-EPMC5460293 | 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