Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Coupling of α,α-difluoro-substituted organozinc reagents with 1-bromoalkynes.

ABSTRACT: α,α-Difluoro-substituted organozinc reagents generated from conventional organozinc compounds and difluorocarbene couple with 1-bromoalkynes affording gem-difluorinated alkynes. The cross-coupling proceeds in the presence of catalytic amounts of copper iodide in dimethylformamide under ligand-free conditions.

SUBMITTER: Zemtsov AA

PROVIDER: S-EPMC4660974 | biostudies-literature | 2015

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Coupling of α,α-difluoro-substituted organozinc reagents with 1-bromoalkynes.

Zemtsov Artem A AA Volodin Alexander D AD Levin Vitalij V VV Struchkova Marina I MI Dilman Alexander D AD

Beilstein journal of organic chemistry 20151110

α,α-Difluoro-substituted organozinc reagents generated from conventional organozinc compounds and difluorocarbene couple with 1-bromoalkynes affording gem-difluorinated alkynes. The cross-coupling proceeds in the presence of catalytic amounts of copper iodide in dimethylformamide under ligand-free conditions. ...[more]

PMID: 26664635

Similar Datasets

Copper(I)-Catalyzed Cross-Coupling of 1-Bromoalkynes with N-Heterocyclic Organozinc Reagents.

Project description:Nitrogen-containing heterocycles represent the majority of FDA-approved small-molecule pharmaceuticals. Herein, we describe a synthetic method to produce saturated N-heterocyclic drug scaffolds with an internal alkyne for elaboration. The treatment of N,N-dimethylhydrazinoalkenes with Et2Zn, followed by a Cu(I)-catalyzed cross-coupling with 1-bromoalkynes, results in piperidines and pyrrolidines with a good yield. Five examples are reported and a proposed mechanism for the Cu(I)-catalyzed cross-coupling is presented.

| S-EPMC9315687 | biostudies-literature

Enantioselective Radical Addition/Cross-Coupling of Organozinc Reagents, Alkyl Iodides, and Alkenyl Boron Reagents.

Project description:A hybrid transition-metal/radical process is described that results in the addition of organozinc reagents and alkyl halides across alkenyl boron reagents in an enantioselective catalytic fashion. The reaction can be accomplished both intermolecularly and intramolecularly, providing useful product yields and high enantioselectivities in both manifolds.

| S-EPMC6764867 | biostudies-literature

Multicomponent synthesis of α-branched amines using organozinc reagents generated from alkyl bromides

Project description: Not available

| S-EPMC11552408 | biostudies-literature

A Synthesis of Substituted α-Allenols via Iron-Catalyzed Cross-Coupling of Propargyl Carboxylates with Grignard Reagents.

Project description:α-Allenols are attractive and versatile compounds whose preparation can be a nontrivial task. In this Letter, we provide a method for the prompt synthesis of substituted α-allenols via a catalytic cross-coupling reaction which makes use of a nontoxic and cost-effective iron catalyst. The catalyst loading is typically as low as 1-5 mol %. The mild reaction conditions (-20 °C) and the short reaction time (15 min) allow for the presence of a variety of functional groups. Moreover, the reaction was shown to be scalable up to gram-scale and the propargyl substrates are readily accessible by a one-pot synthesis.

| S-EPMC5100686 | biostudies-literature

Rh(II)-Catalyzed Reactions of Diazoesters with Organozinc Reagents.

Project description:Rh(II)-catalyzed reactions of diazoesters with organozinc reagents are described. Diorganozinc reagents participate in reactions with diazo compounds by two distinct, catalyst-dependent mechanisms. With bulky diisopropylethyl acetate ligands, the reaction mechanism is proposed to involve initial formation of a Rh-carbene and subsequent carbozincation to give a zinc enolate. With Rh2(OAc)4, it is proposed that initial formation of an azine precedes 1,2-addition by an organozinc reagent. This straightforward route to the hydrazone products provides a useful method for preparing chiral quaternary α-aminoesters or pyrazoles via the Paul-Knorr condensation with 1,3-diketones. Crossover and deuterium labeling experiments provide evidence for the mechanisms proposed.

| S-EPMC4552333 | biostudies-literature

Mechanistic Studies of the TRIP-Catalyzed Allylation with Organozinc Reagents.

Project description:3,3-Bis(2,4,6-triisopropylphenyl)-1,1-binaphthyl-2,2-diyl hydrogenphosphate (TRIP) catalyzes the asymmetric allylation of aldehydes with organozinc compounds, leading to highly valuable structural motifs, like precursors to lignan natural products. Our previously reported mechanistic proposal relies on two reaction intermediates and requires further investigation to really understand the mode of action and the origins of stereoselectivity. Detailed ab initio calculations, supported by experimental data, render a substantially different mode of action to the allyl boronate congener. Instead of a Brønsted acid-based catalytic activation, the chiral phosphate acts as a counterion for the Lewis acidic zinc ion, which provides the activation of the aldehyde.

| S-EPMC7418105 | biostudies-literature

Direct Copper-Free Domino Conjugate Addition-Cycloallylation using Organozinc Reagents.

Project description:The Direct Approach: Enones possessing appendant allylic carbonates react directly with diorganozinc reagents in the presence of zinc diiodide [ZnI(2)] to provide 5- and 6-membered ring products of tandem or domino conjugate addition-cycloallylation in good to excellent yield. In a related copper-free transformation, allylic carbonates are found to engage in direct allylic substitution with diorganozinc reagents.

| S-EPMC2865154 | biostudies-literature

Transition-Metal-Free Synthesis of Polyfunctional Triarylmethanes and 1,1-Diarylalkanes by Sequential Cross-Coupling of Benzal Diacetates with Organozinc Reagents.

Project description:A variety of functionalized triarylmethane and 1,1-diarylalkane derivatives were prepared via a transition-metal-free, one-pot and two-step procedure, involving the reaction of various benzal diacetates with organozinc reagents. A sequential cross-coupling is enabled by changing the solvent from THF to toluene, and a two-step SN 1-type mechanism was proposed and evidenced by experimental studies. The synthetic utility of the method is further demonstrated by the synthesis of several biologically relevant molecules, such as an anti-tuberculosis agent, an anti-breast cancer agent, a precursor of a sphingosine-1-phosphate (S1P) receptor modulator, and a FLAP inhibitor.

| S-EPMC8252654 | biostudies-literature

Synthesis of Heteroaryl Sulfonamides from Organozinc Reagents and 2,4,6-Trichlorophenyl Chlorosulfate.

Project description:A method for the preparation of aryl and heteroaryl sulfonamides using 2,4,6-trichlorophenyl chlorosulfate (TCPC) is described. The reaction of 2-pyridylzinc reagents with TCPC resulted in 2,4,6-trichlorophenyl (TCP) pyridine-2-sulfonates, and the parent pyridine-2-sulfonate was shown to react with amines. Less electron-rich aryl- and heteroarylzinc reagents reacted with TCPC to afford sulfonyl chlorides that were converted in situ to sulfonamides.

| S-EPMC4477900 | biostudies-literature

Iron-catalyzed Cross-Coupling of Propargyl Carboxylates and Grignard Reagents: Synthesis of Substituted Allenes.

Project description:Presented herein is a mild, facile, and efficient iron-catalyzed synthesis of substituted allenes from propargyl carboxylates and Grignard reagents. Only 1-5 mol % of the inexpensive and environmentally benign [Fe(acac)3 ] at -20 °C was sufficient to afford a broad range of substituted allenes in excellent yields. The method tolerates a variety of functional groups.

| S-EPMC4797716 | 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