Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Expanding the horizon of intermolecular trapping of in situ generated ?-oxo gold carbenes: efficient oxidative union of allylic sulfides and terminal alkynes via C-C bond formation.

ABSTRACT: With a new P,S-bidentate phosphine as the ligand to gold(I), the ?-oxo gold carbenes generated in situ via gold-catalyzed intermolecular oxidation of terminal alkynes were effectively trapped by various allylic sulfides, resulting in the formation of ?-aryl(alkyl)thio-?,?-unsaturated ketones upon facile [2,3]sigmatropic rearrangements.

SUBMITTER: Li J

PROVIDER: S-EPMC4090113 | biostudies-literature | 2014 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Expanding the horizon of intermolecular trapping of in situ generated α-oxo gold carbenes: efficient oxidative union of allylic sulfides and terminal alkynes via C-C bond formation.

Li Jiabin J Ji Kegong K Zheng Renhua R Nelson Jonathan J Zhang Liming L

Chemical communications (Cambridge, England) 20140401 31

With a new P,S-bidentate phosphine as the ligand to gold(I), the α-oxo gold carbenes generated in situ via gold-catalyzed intermolecular oxidation of terminal alkynes were effectively trapped by various allylic sulfides, resulting in the formation of α-aryl(alkyl)thio-γ,δ-unsaturated ketones upon facile [2,3]sigmatropic rearrangements. ...[more]

PMID: 24622909

Similar Datasets

Reactivities of α-Oxo BMIDA Gold Carbenes Generated by Gold-Catalyzed Oxidation of BMIDA-Terminated Alkynes.

Project description:An oxidative strategy is reported to access α-oxo BMIDA gold carbenes directly from BMIDA-terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C-H bonds in the absence of the Thorpe-Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F-C alkylations. This chemistry provides rapid access to structurally diverse α-BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron-donating group that attenuates the high electrophilicity of the gold carbene center.

| S-EPMC10079581 | biostudies-literature

Intermolecular Hydroaminoalkylation of Alkynes.

Project description:Intermolecular hydroaminoalkylation reactions of alkynes with secondary amines, which selectively give access to allylic amines with E configuration of the alkene unit, are achieved in the presence of titanium catalysts. Successful reactions of symmetrically substituted diaryl- and dialkylalkynes as well as a terminal alkyne take place with N-benzylanilines, N-alkylanilines, and N-alkylbenzylamines.

| S-EPMC8248392 | biostudies-literature

Silylene transfer to allylic sulfides: formation of substituted silacyclobutanes.

Project description:Silylene transfer to allylic sulfides results in a formal 1,2-sulfide migration. The rearrangement yields substituted silacyclobutanes, not the expected silacyclopropanes. The silacyclobutanes were elaborated by insertions of carbonyl compounds selectively into one carbon-silicon bond. A mechanism for the 1,2-sulfide migration is proposed involving an episulfonium ion intermediate.

| S-EPMC4037888 | biostudies-literature

Alkynes as equivalents of alpha-diazo ketones in generating alpha-oxo metal carbenes: a gold-catalyzed expedient synthesis of dihydrofuran-3-ones.

Project description:An expedient and reliable method for accessing reactive alpha-oxo gold carbenes via gold-catalyzed intermolecular oxidation of terminal alkynes has been developed. Significantly, this method offers a safe and economical alternative to the strategies based on diazo substrates. Its synthetic potential is demonstrated by expedient preparation of dihydrofuran-3-ones containing a broad range of functional groups.

| S-EPMC2847863 | biostudies-literature

Late-Stage Intermolecular Allylic C-H Amination.

Project description:Allylic amination enables late-stage functionalization of natural products where allylic C-H bonds are abundant and introduction of nitrogen may alter biological profiles. Despite advances, intermolecular allylic amination remains a challenging problem due to reactivity and selectivity issues that often mandate excess substrate, furnish product mixtures, and render important classes of olefins (for example, functionalized cyclic) not viable substrates. Here we report that a sustainable manganese perchlorophthalocyanine catalyst, [MnIII(ClPc)], achieves selective, preparative intermolecular allylic C-H amination of 32 cyclic and linear compounds, including ones housing basic amines and competing sites for allylic, ethereal, and benzylic amination. Mechanistic studies support that the high selectivity of [MnIII(ClPc)] may be attributed to its electrophilic, bulky nature and stepwise amination mechanism. Late-stage amination is demonstrated on five distinct classes of natural products, generally with >20:1 site-, regio-, and diastereoselectivity.

| S-EPMC8961995 | biostudies-literature

α-Functionalisation of Cyclic Sulfides Enabled by Lithiation Trapping.

Project description:A general and straightforward procedure for the lithiation trapping of cyclic sulfides such as tetrahydrothiophene, tetrahydrothiopyran and a thiomorpholine is described. Trapping with a wide range of electrophiles is demonstrated, leading to more than 50 diverse α-substituted saturated sulfur heterocycles. The methodology provides access to a range of α-substituted cyclic sulfides that are not easily synthesised by the currently available methods.

| S-EPMC10952194 | 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

Enantioselective imidation of sulfides via enzyme-catalyzed intermolecular nitrogen-atom transfer.

Project description:Engineering enzymes with novel reaction modes promises to expand the applications of biocatalysis in chemical synthesis and will enhance our understanding of how enzymes acquire new functions. The insertion of nitrogen-containing functional groups into unactivated C-H bonds is not catalyzed by known enzymes but was recently demonstrated using engineered variants of cytochrome P450BM3 (CYP102A1) from Bacillus megaterium. Here, we extend this novel P450-catalyzed reaction to include intermolecular insertion of nitrogen into thioethers to form sulfimides. An examination of the reactivity of different P450BM3 variants toward a range of substrates demonstrates that electronic properties of the substrates are important in this novel enzyme-catalyzed reaction. Moreover, amino acid substitutions have a large effect on the rate and stereoselectivity of sulfimidation, demonstrating that the protein plays a key role in determining reactivity and selectivity. These results provide a stepping stone for engineering more complex nitrogen-atom-transfer reactions in P450 enzymes and developing a more comprehensive biocatalytic repertoire.

| S-EPMC4154708 | biostudies-literature

Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols.

Project description:An enantioselective intermolecular coupling of oxygen nucleophiles and allylic alcohols to give β-aryloxycarbonyl compounds is disclosed using a chiral pyridine oxazoline-ligated palladium catalyst under mild conditions. As opposed to the formation of traditional Wacker-type products, enantioselective migratory insertion is followed by β-hydride elimination toward the adjacent alcohol. Deuterium labeling experiments suggest a syn-migratory insertion of the alkene into the Pd-O bond. A broad scope of phenols, various allylic alcohols, and an alkyl hydroperoxide are viable coupling partners in this process.

| S-EPMC5180452 | biostudies-literature

Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin-Catalyzed Doyle-Kirmse Reaction.

Project description:The first example of a biocatalytic [2,3]-sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle-Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C-C bond-forming transformation with high efficiency and product conversions across a variety of sulfide substrates (e.g., aryl-, benzyl-, and alkyl-substituted allylic sulfides) and α-diazo esters. Moreover, the scope of this myoglobin-mediated transformation could be extended to the conversion of propargylic sulfides to give substituted allenes. Active-site mutations proved effective in enhancing the catalytic efficiency of the hemoprotein in these reactions as well as modulating the enantioselectivity, resulting in the identification of the myoglobin variant Mb(L29S,H64V,V68F), which is capable of mediating asymmetric Doyle-Kirmse reactions with an enantiomeric excess up to 71 %. This work extends the toolbox of currently available biocatalytic strategies for the asymmetric formation of carbon-carbon bonds.

| S-EPMC5189672 | 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