Browse
Submit Data
Databases
API
Help

Dataset Information

37 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Gold-catalyzed intramolecular allylation of silyl alkynes induced by silane alcoholysis.

ABSTRACT: The activation of alkynyl allyl silanes with a cationic gold catalyst in the presence of alcohols provides vinyl silanes that contain the allyl group at the beta-position and the alkoxysilyl group in cis-orientation. The bond reorganization process is most consistent with the involvement of a carbocationic intermediate, which undergoes a nucleophilic attack by an alcohol selectively at the silicon center. The cis-vinyl silyl ether products can be further elaborated by ring-closing and cross metathesis to form more substituted 1,4-dienyl silanes.

SUBMITTER: Park S

PROVIDER: S-EPMC2569199 | biostudies-literature | 2006 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Gold-catalyzed intramolecular allylation of silyl alkynes induced by silane alcoholysis.

Park Sangho S Lee Daesung D

Journal of the American Chemical Society 20060801 33

The activation of alkynyl allyl silanes with a cationic gold catalyst in the presence of alcohols provides vinyl silanes that contain the allyl group at the beta-position and the alkoxysilyl group in cis-orientation. The bond reorganization process is most consistent with the involvement of a carbocationic intermediate, which undergoes a nucleophilic attack by an alcohol selectively at the silicon center. The cis-vinyl silyl ether products can be further elaborated by ring-closing and cross meta ...[more]

PMID: 16910645

Similar Datasets

Gold-catalyzed allylation of aryl boronic acids: accessing cross-coupling reactivity with gold.

Project description:A sp(3)-sp(2) C-C cross-coupling reaction catalyzed by gold in the absence of a sacrificial oxidant is described. Vital to the success of this method is the implementation of a bimetallic catalyst bearing a bis(phosphino)amine ligand. A mechanistic hypothesis is presented, and observable transmetalation, C-Br oxidative addition, and C-C reductive elimination in a model gold complex are shown. We expect that this method will serve as a platform for the development of novel transformations involving redox-active gold catalysts.

| S-EPMC4076148 | biostudies-other

Gold(I)-catalyzed enantioselective carboalkoxylation of alkynes.

Project description:A highly enantioselective carboalkoxylation of alkynes catalyzed by cationic (DTBM-MeO-Biphep)gold(I) complexes is reported. Various optically active ?-alkoxyindanone derivatives were obtained in good yields with high enantioselectivities. Furthermore, this methodology was extended to the enantioselective synthesis of 3-methoxycyclopentenones. The reaction is proposed to proceed through an enantioselective cyclization of intermediates containing vinylgold(I) and prochiral oxocarbenium moieties.

| S-EPMC3795527 | 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

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

Photosensitizer-free visible light-mediated gold-catalysed cis-difunctionalization of silyl-substituted alkynes.

Project description:A new photosensitizer-free visible light-mediated gold-catalysed cis-difunctionalization reaction is developed. The reaction was chemoselective towards silyl-substituted alkynes with excellent regioselectivity and good functional group compatibility, giving a series of silyl-substituted quinolizinium derivatives as products. The newly synthesized fluorescent quinolizinium compounds, named JR-Fluor-1, possessed tunable emission properties and large Stokes shifts. With unique photophysical properties, the fluorophores have been applied in photooxidative amidations as efficient photocatalysts and cellular imaging with switchable subcellular localization properties.

| S-EPMC5676248 | biostudies-literature

Gold(I)-catalyzed intramolecular hydroarylation of allenes.

Project description:Gold(I) complexes react with 4-allenyl arenes in an exo fashion to furnish vinyl-substituted benzocycles. Phosphite gold(I) monocations were found to be optimal, and the catalyst was tolerant of ethers, esters, and pyrroles. Reactions proceeded in unpurified solvent at room temperature.

| S-EPMC2924810 | biostudies-literature

Gold(I)-Catalyzed Nucleophilic Allylation of Azinium Ions with Allylboronates.

Project description:Gold(I)-catalyzed nucleophilic allylations of pyridinium and quinolinium ions with various allyl pinacolboronates are reported. The reactions are completely selective with respect to the site of the azinium ion that is attacked, to give various functionalized 1,4-dihydropyridines and 1,4-dihydroquinolines. Evidence suggests that the reactions proceed through nucleophilic allylgold(I) intermediates formed by transmetalation from allylboronates. Density functional theory (DFT) calculations provided mechanistic insight.

| S-EPMC9314030 | biostudies-literature

Synthesis of Functionalized 3<i>H</i>-pyrrolo-[1,2,3-<i>de</i>] Quinoxalines via Gold-Catalyzed Intramolecular Hydroamination of Alkynes.

Project description:A gold-catalyzed protocol to obtain functionalized 3H-pyrrolo [1,2,3-de] quinoxalines from suitable substituted N-alkynyl indoles has been proposed. The mild reaction conditions were revealed to be compatible with different functional groups, including halogen, alkoxyl, cyano, ketone, and ester, allowing the isolation of title compounds with yields from good to high. A reaction mechanism has been proposed, and theoretical calculations have been provided to rationalize the final step of the hypothesized reaction mechanism. As quinoxaline-containing polycyclic compounds, this class of molecules may represent a valuable template in medicinal chemistry and material science.

| S-EPMC10421283 | biostudies-literature

Chloride-Tolerant Gold(I)-Catalyzed Regioselective Hydrochlorination of Alkynes.

Project description:We have developed a highly regioselective homogeneous gold(I)-catalyzed anti-hydrochlorination of unactivated alkynes at room temperature. We have overcome the incompatibility between conventional cationic gold catalysts and chloride by using a hydrogen-bonding activation of the Au-Cl bond. This approach is scalable, exhibits excellent functional group tolerance, and can be conducted in open air.

| S-EPMC5634393 | biostudies-literature

Rhodium(III)-Catalyzed Intramolecular Annulations of Acrylic and Benzoic Acids to Alkynes.

Project description:Rh(III) catalysts can promote a formal (4 + 2) intramolecular oxidative annulation between acrylic or benzoic acid derivatives and alkynes. The reaction, which involves a C-H activation process, allows for a rapid assembly of appealing bicyclic pyran-2-ones and tricyclic isocoumarin derivatives in moderate to good yields. The α-pyrone moiety of the products provides for further manipulations to obtain relatively complex cyclic skeletons in a very simple manner.

| S-EPMC6492232 | 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