Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Gold-catalyzed reaction of oxabicyclic alkenes with electron-deficient terminal alkynes to produce acrylate derivatives.

ABSTRACT: Oxabicyclic alkenes can react with electron-deficient terminal alkynes in the presence of a gold catalyst under mild conditions, affording the corresponding addition products in moderate yields. When using alkynyl esters as substrates, the (Z)-acrylate derivatives are obtained. Using but-3-yn-2-one (ethynyl ketone) as a substrate, the corresponding addition product is obtained with (E)-configuration. The proposed mechanism of these reactions is also discussed.

SUBMITTER: Sun YW

PROVIDER: S-EPMC3817539 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Gold-catalyzed reaction of oxabicyclic alkenes with electron-deficient terminal alkynes to produce acrylate derivatives.

Sun Yin-Wei YW Xu Qin Q Shi Min M

Beilstein journal of organic chemistry 20131001

Oxabicyclic alkenes can react with electron-deficient terminal alkynes in the presence of a gold catalyst under mild conditions, affording the corresponding addition products in moderate yields. When using alkynyl esters as substrates, the (Z)-acrylate derivatives are obtained. Using but-3-yn-2-one (ethynyl ketone) as a substrate, the corresponding addition product is obtained with (E)-configuration. The proposed mechanism of these reactions is also discussed. ...[more]

PMID: 24204408

Similar Datasets

Synthesis of Isomerically Pure (Z)-Alkenes from Terminal Alkynes and Terminal Alkenes: Silver-Catalyzed Hydroalkylation of Alkynes.

Project description:Alkenes are an important class of compounds common among biologically active molecules and often are used as intermediates in organic synthesis. Many alkenes exist in two stereoisomeric forms (E and Z), which have different structures and different properties. The selective formation of the two isomers is an important synthetic goal that has long inspired the development of new synthetic methods. However, the efficient synthesis of diastereopure, thermodynamically less stable, Z-alkenes is still challenging. Here, we demonstrate an efficient synthesis of diastereopure Z-alkenes (Z:E > 300:1) through a silver-catalyzed hydroalkylation of terminal alkynes, using alkylboranes as coupling partners. We also describe the exploration of the substrate scope, which reveals the broad functional group compatibility of the new method. Preliminary mechanistic studies suggest that a 1,2-metalate rearrangement of the silver borate intermediate is the key step responsible for the stereochemical outcome of the reaction.

| S-EPMC7304281 | biostudies-literature

Copper-Catalyzed Oxidative Cross-Coupling of Electron-Deficient Polyfluorophenylboronate Esters with Terminal Alkynes.

Project description:We report herein a mild procedure for the copper-catalyzed oxidative cross-coupling of electron-deficient polyfluorophenylboronate esters with terminal alkynes. This method displays good functional group tolerance and broad substrate scope, generating cross-coupled alkynyl(fluoro)arene products in moderate to excellent yields. Thus, it represents a simple alternative to the conventional Sonogashira reaction.

| S-EPMC7821263 | biostudies-literature

Gold-Catalyzed Regioselective Dimerization of Aliphatic Terminal Alkynes.

Project description:A gold-catalyzed regioselective homodimerization of aliphatic terminal alkynes is described. Bulky and less Lewis acidic tBuXPhosAuNTf(2) is the preferred catalyst, and the additive, anhydrous NaOAc, substantially facilitates the reaction.

| S-EPMC3419542 | biostudies-literature

Rhodium-catalyzed enantioselective cyclopropanation of electron deficient alkenes.

Project description:The rhodium-catalyzed reaction of electron-deficient alkenes with substituted aryldiazoacetates and vinyldiazoacetates results in highly stereoselective cyclopropanations. With adamantylglycine derived catalyst Rh2(S-TCPTAD)4, high asymmetric induction (up to 98% ee) can be obtained with a range of substrates. Computational studies suggest that the reaction is facilitated by weak interaction between the carbenoid and the substrate carbonyl but subsequently proceeds via different pathways depending on the nature of the carbonyl.. Acrylates and acrylamides result in the formation of cyclopropanation products while the use of unsaturated aldehydes and ketones results in the formation of epoxides.

| S-EPMC3773518 | 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

Gold-Catalyzed Vinyl Ether Hydroalkynylation: An Alternative Pathway for the Gold-Catalyzed Intermolecular Reaction of Alkenes and Alkynes.

Project description:In this report, the gold-catalyzed intermolecular reaction of vinyl ethers and terminal alkynes is investigated. Utilizing a triazole gold catalyst lessens gold decomposition in the presence of the vinyl ether and affords an alkynylation product instead of the [2 + 2] product. This protocol has been expanded to include glycal substrates, which undergo a one-pot alkynylation-Ferrier reaction to produce functionalized sugars in moderate to excellent yields with high diastereoselectivity.

| S-EPMC6430632 | biostudies-literature

Iron-catalyzed carboazidation of alkenes and alkynes.

Project description:Carboazidation of alkenes and alkynes holds the promise to construct valuable molecules directly from chemical feedstock therefore is significantly important. Although a few examples have been developed, there are still some unsolved problems and lack of universal methods for carboazidation of both alkenes and alkynes. Here we describe an iron-catalyzed rapid carboazidation of alkenes and alkynes, enabled by the oxidative radical relay precursor t-butyl perbenzoate. This strategy enjoys success with a broad scope of alkenes under mild conditions, and it can also work with aryl alkynes which are challenging substrates for carboazidation. A large number of diverse structures, including many kinds of amino acid precursors, fluoroalkylated vinyl azides, other specific organoazides, and 2H-azirines can be easily produced.

| S-EPMC6328574 | biostudies-literature

Hydroboration of Terminal Alkenes and trans-1,2-Diboration of Terminal Alkynes Catalyzed by a Manganese(I) Alkyl Complex.

Project description:A MnI -catalyzed hydroboration of terminal alkenes and a 1,2-diboration of terminal alkynes with pinacolborane (HBPin) is described. For alkenes, anti-Markovnikov hydroboration takes place; for alkynes the reaction proceeds with excellent trans-1,2-selectivity. The most active pre-catalyst is bench-stable alkyl bisphosphine MnI complex fac-[Mn(dippe)(CO)3 (CH2 CH2 CH3 )]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate, which undergoes B-H bond cleavage of HBPin (for alkenes) and rapid C-H bond cleavage (for alkynes), forming the active MnI boryl and acetylide catalysts [Mn(dippe)(CO)2 (BPin)] and [Mn(dippe)(CO)2 (C≡CR)], respectively. A broad variety of aromatic and aliphatic alkenes and alkynes was efficiently and selectively borylated. Mechanistic insights are provided based on experimental data and DFT calculations revealing that an acceptorless reaction is operating involving dihydrogen release.

| S-EPMC8596825 | biostudies-literature

Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with secondary amine nucleophiles.

Project description:Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with various aliphatic and aromatic secondary amines are reported for the first time. The reaction gave the corresponding trans-1,2-dihydronaphthalenol derivatives in good yields with moderate enantioselectivities in the presence of 2.5 mol % [Ir(COD)Cl](2) and 5 mol % bisphosphine ligand (S)-p-Tol-BINAP. The trans-configuration of 3f was confirmed by X-ray crystallography.

| S-EPMC2814328 | biostudies-literature

Cobalt-Catalyzed Hydrogen-Atom Transfer Induces Bicyclizations that Tolerate Electron-Rich and Electron-Deficient Intermediate Alkenes.

Project description:A novel CoII -catalyzed polyene cyclization was developed that is uniquely effective when performed in hexafluoroisopropanol as the solvent. The process is presumably initiated by metal-catalyzed hydrogen-atom transfer (MHAT) to 1,1-disubstituted or monosubstituted alkenes, and the reaction is remarkable for its tolerance of internal alkenes bearing either electron-rich methyl or electron-deficient nitrile substituents. Electron-rich aromatic terminators are required in both cases. Terpenoid scaffolds with different substitution patterns are obtained with excellent diastereoselectivities, and the bioactive C20-oxidized abietane diterpenoid carnosaldehyde was made to showcase the utility of the nitrile-bearing products. Also provided are the results of several mechanistic experiments that suggest the process features an MHAT-induced radical bicyclization with late-stage oxidation to regenerate the aromatic terminator.

| S-EPMC7124983 | 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