Browse
Submit Data
Databases
API
Help

Dataset Information

43 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chemoselective hydroamination of vinyl arenes catalyzed by an NHC-amidate-alkoxide Pd(II) complex and p-TsOH.

ABSTRACT: The hydroamination of various substituted vinyl arenes with benzenesulfonamide was explored using an NHC-amidate-alkoxide palladium catalyst in conjunction with p-TsOH. Utilizing halide-substituted and electron-rich vinyl arenes, this methodology selectively furnished the cross-coupled hydroamination products in moderate to excellent yields in a Markovnikov fashion while greatly reducing undesired acid-catalyzed homocoupling of the vinyl arenes. Electron-rich vinyl arenes typically required milder conditions than electron-poor ones. While most effective for para-substituted substrates, the catalyst system also furnished the desired products from ortho- and meta-substituted vinyl arenes with high chemoselectivities.

SUBMITTER: Giles R

PROVIDER: S-EPMC3768155 | biostudies-literature | 2013 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Chemoselective hydroamination of vinyl arenes catalyzed by an NHC-amidate-alkoxide Pd(II) complex and <i>p</i>-TsOH.

Giles Richard R O'Neill Justin J Lee Joo Ho JH Chiu Michael K MK Jung Kyung Woon KW

Tetrahedron letters 20130701 31

The hydroamination of various substituted vinyl arenes with benzenesulfonamide was explored using an NHC-amidate-alkoxide palladium catalyst in conjunction with <i>p</i>-TsOH. Utilizing halide-substituted and electron-rich vinyl arenes, this methodology selectively furnished the cross-coupled hydroamination products in moderate to excellent yields in a Markovnikov fashion while greatly reducing undesired acid-catalyzed homocoupling of the vinyl arenes. Electron-rich vinyl arenes typically requir ...[more]

PMID: 24039309

Similar Datasets

Iodine-Catalyzed Chemoselective Hydroamination Reaction Using 5-Mercaptotetrazoles Derivatives.

Project description:Metal-free chemoselective hydroamination of styrene derivatives has been achieved with high chemoselectivity over sulfenylation of 1H-tetrazole-5-thiol using a catalytic amount of iodine. The scope of this methodology has been extended for the hydroamination of α-substituted styrene derivatives. This reaction involves a single-step C-N-bond formation under atom economical process. This eco-friendly method uses readily available and inexpensive iodine in a catalytic amount.

| S-EPMC6641749 | biostudies-literature

Asymmetric intermolecular boron Heck-type reactions via oxidative palladium(II) catalysis with chiral tridentate NHC-amidate-alkoxide ligands.

Project description:Chiral dimeric tridentate NHC-amidate-alkoxide palladium(II) complexes, 3a and 3b, effected oxidative boron Heck-type reactions of aryl boronic acids with both acyclic and cyclic alkenes at room temperature to afford the corresponding coupling products with high enantioselectivities. The high degree of enantioselection, far superior to existing methods, stems from differences in the nonbonding interactions in the proposed transition states, due to the influence from bulky substituents of the alkene substrates and the "counter axial groups" of the palladium(II) catalysts.

| S-EPMC2798920 | biostudies-literature

Iron catalyzed methylation and ethylation of vinyl arenes.

Project description:Short alkyl chain Heck (type) reactions, especially methyl Heck reactions, are a difficult aspect of the alkyl Heck reaction. To provide a solution to this problem, iron-catalyzed methyl, ethyl and propyl Heck reactions were developed using readily available alkyl peroxides as alkyl sources. The reaction conditions were mild, clean, and easy to handle. No additive was needed, and no hazardous waste was generated. The products were obtained in up to 99% yield of one isomer for most situations. This reaction works for many types of olefin and tolerates a variety of functional groups. Several late-stage functionalizations of natural products and drug molecules were conducted to demonstrate the synthetic applications of this reaction.

| S-EPMC5399631 | biostudies-literature

Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

Project description:We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

| S-EPMC3978782 | biostudies-literature

Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map.

Project description:Generally, N-heterocyclic carbene (NHC) complexed with carbonyl compounds would transform into several important active intermediates, i.e., enolates, Breslow intermediates, or acylazolium intermediates, which act as either a nucleophile (Nu) or an electrophile (E) to react with the other E/Nu partner. Hence, the key to predicting the origin of chemoselectivity is to compute the activity (i.e., electrophilic index ω for E and nucleophilic index N for Nu) and stability of the intermediates and products, which are suggested in a general mechanistic map of these reactions. To support this point, we selected and studied different cases of the NHC-catalyzed reactions of carbonyl compounds in the presence of a base and/or an oxidant, in which multiple possible pathways involving acylazolium, enolate, Breslow, and α,β-unsaturated acylazolium intermediates were proposed and a novel index ω + N of the E and Nu partners was employed to exactly predict the energy barrier of the chemoselective step in theory. This work provides a guide for determining the general principle behind organocatalytic reactions with various chemoselectivities, and suggests a general application of the reaction index in predicting the chemoselectivity of the nucleophilic and electrophilic reactions.

| S-EPMC8159411 | biostudies-literature

Chemoselective hydrogenation of heteroarenes and arenes by Pd-Ru-PVP under mild conditions.

Project description:Monometallic (Pd, Ru or Rh) and bimetallic (Pd0.5-Ru0.5) alloy NPs catalysts were examined for the hydrogenation of quinoline. Pd-Ru alloy catalyst showed superior catalytic activity to the traditional Rh catalyst. The characterization of Pd0.5-Ru0.5 catalysts, HAADF-EDX mapping and XPS analysis suggested that the alloy state of PdRu catalysts remained unchanged in the recovered catalyst. Furthermore, the catalyst was highly selective for the hydrogenation of different arenes.

| S-EPMC9058507 | biostudies-literature

Pd-Catalyzed Hydroamination of Alkoxyallenes with Azole Heterocycles: Examples and Mechanistic Proposal.

Project description:Palladium-catalyzed regio- and enantioselective addition of azole heterocycles to alkoxyallenes was developed (up to 92% yields and up to 94% ee). DFT calculations suggest a new Pd(0)-driven mechanistic pathway proceeding through protonation of the Pd-coordinated allene (4-PdL2), which develops a strongly nucleophilic character at the central C atom.

| S-EPMC5565904 | biostudies-literature

Hydroamination of Aromatic Alkynes to Imines Catalyzed by Pd(II)-Anthraphos Complexes.

Project description:Herein, we report the synthesis, characterization, and catalytic performance of cationic Pd(II)-Anthraphos complexes in the intermolecular hydroamination of aromatic alkynes with aromatic amines. The reaction proceeds with 0.18 mol % of catalyst loading, at 90 °C for 4 h under neat conditions. Good to excellent yields could be obtained for a broad range of amines and alkynes.

| S-EPMC7178791 | biostudies-literature

Pd(II)-Catalyzed C3-Selective Arylation of Pyridine with (Hetero)arenes.

Project description:Palladium catalyzed, nondirected C3-selective arylation of pyridines with arenes and heteroarenes in the presence of 1,10-phenanthroline as the ligand has been developed. The optimized conditions allow for a highly C3-selective arylation of pyridines, affording various 3,3'-bipyridines and 3-arylpyridines.

| S-EPMC4821414 | biostudies-literature

Pd(II)-catalyzed para-selective C-H arylation of monosubstituted arenes.

Project description:Pd-catalyzed highly para-selective C-H arylation of monosubstituted arenes (including toluene) is developed for the first time using an F(+) reagent as a bystanding oxidant. This finding provides a new retrosynthetic disconnection for para-substituted biaryl synthesis via C-H/C-H cross-coupling.

| S-EPMC3345815 | 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