Browse
Submit Data
Databases
API
Help

Dataset Information

31 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Copper(II)-catalyzed silylation of activated alkynes in water: diastereodivergent access to E- or Z-?-silyl-?,?-unsaturated carbonyl and carboxyl compounds.

ABSTRACT: Copper(II)-catalyzed silylation of substituted alkynylcarbonyl compounds was investigated. Through the activation of Me2 PhSiBpin in water at room temperature and open atmosphere, vinylsilanes conjugated to carbonyl groups are synthesized in high yield. A surprising diastereodivergent access to olefin geometry was discovered using a silyl conjugate addition strategy: aldehydes and ketones were Z selective while esters and amides were exclusively transformed into the E?products.

SUBMITTER: Calderone JA

PROVIDER: S-EPMC4035118 | biostudies-literature | 2014 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Copper(II)-catalyzed silylation of activated alkynes in water: diastereodivergent access to E- or Z-β-silyl-α,β-unsaturated carbonyl and carboxyl compounds.

Calderone Joseph A JA Santos Webster L WL

Angewandte Chemie (International ed. in English) 20140214 16

Copper(II)-catalyzed silylation of substituted alkynylcarbonyl compounds was investigated. Through the activation of Me2 PhSiBpin in water at room temperature and open atmosphere, vinylsilanes conjugated to carbonyl groups are synthesized in high yield. A surprising diastereodivergent access to olefin geometry was discovered using a silyl conjugate addition strategy: aldehydes and ketones were Z selective while esters and amides were exclusively transformed into the E products. ...[more]

PMID: 24532188

Similar Datasets

Copper-catalyzed ?-boration of ?,?-unsaturated carbonyl compounds with tetrahydroxydiborane.

Project description:The copper-catalyzed ?-boration of ?,?-unsaturated carbonyl compounds with tetrahydroxydiborane has been developed. This diboron reagent allows direct, efficient access to boronic acids and their derivatives. Primary, secondary, and tertiary ?,?-unsaturated amides are converted to the corresponding ?-trifluoroboratoamides in good to excellent yields. The ?-boration of a variety of ?,?-unsaturated esters and ketones is also reported.

| S-EPMC3162992 | biostudies-literature

Copper-Catalyzed Asymmetric Silylation of Propargyl Dichlorides: Access to Enantioenriched Functionalized Allenylsilanes.

Project description:A copper-catalyzed silylation of propargyl dichlorides was developed to access chloro-substituted allenylsilanes under mild reaction conditions. Moreover, enantioenriched chloro-substituted allenylsilanes can be synthesized in moderate to high yields and good enantioselectivities with this protocol.

| S-EPMC6899605 | biostudies-literature

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

Project description: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.

| S-EPMC2569199 | biostudies-literature

Copper-catalyzed cascade annulation of unsaturated ?-bromocarbonyls with enynals: a facile access to ketones from aldehydes.

Project description:A Cu-catalyzed cascade annulation of enynals with alkenyl or alkynyl ?-bromocarbonyls for the synthesis of various cyclohexenone-fused polycyclic compounds is described. Up to six new C-C bonds and four new carbocycles can be established in a single reaction, highlighting the high efficiency and step-economics of this protocol. This reaction offers a novel and straightforward entry to the synthesis of ketones featuring the addition of carbon radicals to aldehydes.

| S-EPMC6014112 | biostudies-literature

Gold-catalyzed nitrene transfer to activated alkynes: formation of ?,?-unsaturated amidines.

Project description:A gold-catalyzed intermolecular nitrene transfer to alkynes was developed for the first time, revealing a new mode of nitrene transfer and providing a novel access to versatile ?-imino metal carbenes. Various mild nitrene-transfer reagents were examined, and iminopyridium ylides especially those based on 3,5-dichloropyridine proved be highly effective. With activated alkynes such as N-alkynyloxazolidinones as substrates, ?,?-unsaturated amidines were formed in mostly good yields.

| S-EPMC3085905 | biostudies-literature

Stereospecific and Chemoselective Copper-Catalyzed Deaminative Silylation of Benzylic Ammonium Triflates.

Project description:A method for the synthesis of benzylsilanes starting from the corresponding ammonium triflates is reported. Silyl boronic esters are employed as silicon pronucleophiles, and the reaction is catalyzed by copper(I) salts. Enantioenriched benzylic ammonium salts react stereospecifically through an SN 2-type displacement of the ammonium group to afford ?-chiral silanes with inversion of the configuration. A cyclopropyl-substituted substrate does not undergo ring opening, thus suggesting an ionic reaction mechanism with no benzyl radical intermediate.

| S-EPMC7003868 | biostudies-literature

Activation of Si-Si Bonds for Copper(I)-Catalyzed Conjugate Silylation.

Project description:Several alkyl- and vinylsilanes were prepared through the copper(I)-catalyzed conjugate silylation of ?,?-unsaturated compounds. Optimal reaction conditions were first investigated to realize the conjugate addition of a nucleophilic silicon species to poorly electrophilic acceptors such as phenylvinyl sulfone by cleavage of the Si-Si bond of a disilane reagent. The scope of this reaction was extended to various electrophiles bearing different electron-withdrawing groups and afforded the desired substituted alkyl- and vinylsilanes. Among the wide range of commercially available disilanes, the reactivities of alkyl-, aryl-, and ethoxydisilane were also examined.

| S-EPMC3510700 | biostudies-literature

Copper-catalyzed dehydrogenative borylation of terminal alkynes with pinacolborane.

Project description:LCuOTf complexes [L = cyclic (alkyl)(amino)carbenes (CAACs) or N-heterocyclic carbenes (NHCs)] selectively promote the dehydrogenative borylation of C(sp)-H bonds at room temperature. It is shown that ?,?-bis(copper) acetylide and copper hydride complexes are the key catalytic species.

| S-EPMC5308285 | biostudies-other

Copper-catalyzed silylation of p-quinone methides: new entry to dibenzylic silanes.

Project description:An efficient and general copper(I)-catalyzed silylation of p-quinone-methides is described. Non-symmetric dibenzylic silanes are obtained in high yields under mild reaction conditions. These compounds can be used as bench-stable benzylic carbanion precursors.

| S-EPMC4847169 | biostudies-literature

Copper catalyzed borocarbonylation of benzylidenecyclopropanes through selective proximal C-C bond cleavage: synthesis of γ-boryl-γ,δ-unsaturated carbonyl compounds.

Project description:A copper catalyzed borocarbonylation of BCPs via proximal C-C bond cleavage for the synthesis of γ-boryl-γ,δ-unsaturated carbonyl compounds has been developed. Using substituted benzylidenecyclopropanes (BCPs) and chloroformates as starting material, a broad range of γ-boryl-γ,δ-unsaturated esters were prepared in moderate to excellent yields with excellent regio- and stereoselectivity. Besides, when aliphatic acid chlorides were used in this reaction, γ-boryl-γ,δ-unsaturated ketones could be produced in excellent yields. When substituted BCPs were used as substrates, the borocarbonylation occurred predominantly at the proximal C-C bond trans to the phenyl group in a regio- and stereoselective manner, which leads to the Z-isomers as the products. This efficient methodology involves the cleavage of a C-C bond and the formation of a C-C bond as well as a C-B bond, and provides a new method for the proximal C-C bond difunctionalization of BCPs.

| S-EPMC9214919 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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