Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Silver-Catalyzed Stereoselective Aminosulfonylation of Alkynes.

ABSTRACT: 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.

SUBMITTER: Ning Y

PROVIDER: S-EPMC5655761 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Silver-Catalyzed Stereoselective Aminosulfonylation of Alkynes.

Ning Yongquan Y Ji Qinghe Q Liao Peiqiu P Anderson Edward A EA Bi Xihe X

Angewandte Chemie (International ed. in English) 20170707 44

A silver-catalyzed intermolecular aminosulfonylation of terminal alkynes with sodium sulfinates and TMSN<sub>3</sub> 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 β-sulfonyl enamines without electron-withdrawing groups on the nitrogen atom. These enamines are found to be suitable for a variety of furthe ...[more]

PMID: 28627090

Similar Datasets

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

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

Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

Project description:We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

| S-EPMC3837490 | biostudies-literature

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

Project description: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.

| S-EPMC5745071 | 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

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

Silver-catalyzed stereoselective formation of glycosides using glycosyl ynenoates as donors.

Project description:A silver-catalyzed glycosylation reaction employing readily accessible and stable glycosyl ynenoates is developed. This reaction is mostly high yielding and exhibits varying levels of stereoinversion at the anomeric position. Compared to established and versatile Yu's gold catalysis, this chemistry features the use of substantially cheaper AgNTf2.

| S-EPMC6080613 | biostudies-literature

Stereoselective Synthesis of Tertiary Allylic Amines by Titanium-Catalyzed Hydroaminoalkylation of Alkynes with Tertiary Amines.

Project description:Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines take place in the presence of catalytic amounts of TiBn4 , Ph3 C[B(C6 F5 )4 ], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary β,γ-disubstituted allylic amines, are formed in convincing yields and with excellent stereoselectivity. Particularly promising for future applications is the fact that even the industrial side product trimethylamine can be used as a substrate.

| S-EPMC9303398 | biostudies-literature

Substrate-Controlled Product Divergence: Silver-Catalyzed Reaction of Trifluoromethyl Ketones with Terminal Alkynes.

Project description:A distinct dichotomy in product distribution was initially observed in the silver-catalyzed reaction of trifluoromethyl (CF3) ketones with terminal alkynes having two different types of electronic natures. The domino reaction smoothly proceeded almost exclusively with high stereoselectivity with terminal alkynes containing ester groups, whereas alkynylation occurred in good yield when terminal alkynes containing aryl or alkyl groups were present. The results indicated that the electronic nature of terminal alkynes can act as a switch that enables either the domino reaction or alkynylation between terminal alkynes and CF3 ketones.

| S-EPMC6640928 | biostudies-literature

Rhodium(i)-catalyzed stereoselective [4+2] cycloaddition of oxetanols with alkynes through C(sp3)-C(sp3) bond cleavage.

Project description:An efficient and convenient synthesis of highly functionalized dihydropyrans has been achieved through rhodium(i)-catalysed tandem C(sp3)-C(sp3) bond cleavage and annulation of oxetanols with alkynes. An enantioselective version was enabled using a Binaphine ligand. Excellent site-selectivity and remarkable enantioretention are obtained for 2-substituted oxetanols.

| S-EPMC5380880 | biostudies-other

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