Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Non-precious metals catalyze formal [4 + 2] cycloaddition reactions of 1,2-diazines and siloxyalkynes under ambient conditions.

ABSTRACT: Copper(I) and nickel(0) complexes catalyze the formal [4 + 2] cycloaddition reactions of 1,2-diazines and siloxyalkynes, a reaction hitherto best catalyzed by silver salts. These catalysts based on earth abundant metals are not only competent, but the copper catalyst, in particular, promotes cycloadditions of pyrido[2,3-d]pyridazine and pyrido[3,4-d]pyridazine, enabling a new synthesis of quinoline and isoquinoline derivatives, as well as the formal [2 + 2] cycloaddition reaction of cyclohexenone with a siloxyalkyne.

SUBMITTER: Sumaria CS

PROVIDER: S-EPMC4076001 | biostudies-literature | 2014 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Non-precious metals catalyze formal [4 + 2] cycloaddition reactions of 1,2-diazines and siloxyalkynes under ambient conditions.

Sumaria Chintan S CS Türkmen Yunus E YE Rawal Viresh H VH

Organic letters 20140609 12

Copper(I) and nickel(0) complexes catalyze the formal [4 + 2] cycloaddition reactions of 1,2-diazines and siloxyalkynes, a reaction hitherto best catalyzed by silver salts. These catalysts based on earth abundant metals are not only competent, but the copper catalyst, in particular, promotes cycloadditions of pyrido[2,3-d]pyridazine and pyrido[3,4-d]pyridazine, enabling a new synthesis of quinoline and isoquinoline derivatives, as well as the formal [2 + 2] cycloaddition reaction of cyclohexenon ...[more]

PMID: 24911346

Similar Datasets

Synthesis of pyrrolo[1,2-<i>a</i>]quinolines by formal 1,3-dipolar cycloaddition reactions of quinolinium salts.

Project description:Quinolinium salts, Q+-CH2-CO2Me Br- and Q+-CH2-CONMe2 Br- (where Q = quinoline), were prepared from quinolines. Deprotonation of these salts with triethylamine promoted the reaction of the resulting quinolinium ylides (formally azomethine ylides) with electron-poor alkenes by conjugate addition followed by cyclization or by [3 + 2] dipolar cycloaddition. The pyrroloquinoline products were formed as single regio- and stereoisomers. These could be converted to other derivatives by Suzuki-Miyaura coupling, reduction or oxidation reactions.

| S-EPMC6633155 | biostudies-literature

Silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes.

Project description:A highly effective silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes has been developed. The reactions provide ready access to a wide range of siloxy naphthalenes and anthracenes, which are formed in good to high yields, under mild reaction conditions, using low catalyst loadings.

| S-EPMC3415592 | biostudies-literature

Enhancing the reactivity of 1,2-diphospholes in cycloaddition reactions.

Project description:Two different approaches have been employed to enhance the reactivity of 1-alkyl-1,2-diphospholes - the introduction of electron-withdrawing groups either at the phosphorus atoms or in the para-position of the arene ring. The alkylation of sodium 1,2-diphospha-3,4,5-triphenylcyclopentadienide with alkyl halides Hal-CH2-R (R = CN, COOEt, OMe, CH2OEt) results in corresponding 1-alkyl-3,4,5-triphenyl-1,2-diphospholes (alkyl = CH2CN (1a), CH2COOEt (1b), CH2OMe (1c), and (CH2)2OEt (1d)), which spontaneously undergo the intermolecular [4 + 2] cycloaddition reactions at room temperature to form the mixture of the cycloadducts, 2a-c, respectively. However the alkylation of sodium 1,2-diphospha-3,4,5-tri(p-fluorophenyl)cyclopentadienide with ethyl iodide leads to stable 1-ethyl-3,4,5-tris(p-fluorophenyl)-1,2-diphosphole (1e), which forms the [4 + 2] cycloadduct 2,3,4,4a,5,6-hexa(p-fluorophenyl)-1-ethyl-1,7,7a-triphospha-4,7-(ethylphosphinidene)indene (2e) only upon heating up to 60 °C. With further heating to 120 °C with N-phenylmaleimide, the cycloadducts 2a-c and 2e undergo the retro-Diels-Alder reaction and form only one product of the [4 + 2] cycloaddition reaction 3a-с, 3e with good yields up to 65%.

| S-EPMC4362055 | biostudies-literature

Asymmeric formal [3 + 3]-cycloaddition reactions of nitrones with electrophilic vinylcarbene intermediates.

Project description:With metal carbene access to dipolar intermediates, 3,6-dihydro-1,2-oxazines are produced in high yields by dirhodium(II) carboxylate catalyzed reactions between nitrones and a β-TBSO-substituted vinyldiazoacetate. High enantiocontrol occurs with catalysis by N-phthaloyl-(S)-(amino acid)-ligated dirhodium carboxylates for [3 + 3]-cycloaddition reactions with both acyclic and cyclic nitrones.

| S-EPMC3192303 | biostudies-literature

Bioreduction of precious and heavy metals by Candida species under oxidative stress conditions.

Project description:The aim of the present work was to evaluate whether Candida species can reduce both precious and toxic pure metals from the respective molecular ions. From these results, the nanoparticles formed were studied using scanning electron microscopy with energy-dispersive spectroscopy, Raman spectroscopy, X-ray fluorescence spectroscopy and synchrotron radiation. Our results showed that the metal ions were reduced to their corresponding metallic nanoconglomerate or nanoparticles by Candida species. This is the first report on how yeasts of this genus are capable of achieving homeostasis (resilience) in the presence of metal ions of both precious and toxic metals by reducing them to a metallic state.

| S-EPMC6801149 | biostudies-literature

1,2-Addition and cycloaddition reactions of niobium bis(imido) and oxo imido complexes.

Project description:The bis(imido) complexes (BDI)Nb(N t Bu)2 and (BDI)Nb(N t Bu)(NAr) (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate; Ar = 2,6-diisopropylphenyl) were shown to engage in 1,2-addition and [2 + 2] cycloaddition reactions with a wide variety of substrates. Reaction of the bis(imido) complexes with dihydrogen, silanes, and boranes yielded hydrido-amido-imido complexes via 1,2-addition across Nb-imido π-bonds; some of these complexes were shown to further react via insertion of carbon dioxide to give formate-amido-imido products. Similarly, reaction of (BDI)Nb(N t Bu)2 with tert-butylacetylene yielded an acetylide-amido-imido complex. In contrast to these results, many related mono(imido) Nb BDI complexes do not exhibit 1,2-addition reactivity, suggesting that π-loading plays an important role in activating the Nb-N π-bonds toward addition. The same bis(imido) complexes were also shown to engage in [2 + 2] cycloaddition reactions with oxygen- and sulfur-containing heteroallenes to give carbamate- and thiocarbamate-imido complexes: some of these complexes readily dimerized to give bis-μ-sulfido, bis-μ-iminodicarboxylate, and bis-μ-carbonate complexes. The mononuclear carbamate imido complex (BDI)Nb(NAr)(N( t Bu)CO2) (12) could be induced to eject tert-butylisocyanate to generate a four-coordinate terminal oxo imido intermediate, which could be trapped as the five-coordinate pyridine or DMAP adduct. The DMAP adducted oxo imido complex (BDI)NbO(NAr)(DMAP) (16) was shown to engage in 1,2-addition of silanes across the Nb-oxo π-bond; this represents a new reaction pathway in group 5 chemistry.

| S-EPMC8162998 | biostudies-literature

Ferrocenyl-substituted tetrahydrothiophenes via formal [3 + 2]-cycloaddition reactions of ferrocenyl thioketones with donor-acceptor cyclopropanes.

Project description:Ferrocenyl thioketones reacted with donor-acceptor cyclopropanes in dichloromethane at room temperature in the presence of catalytic amounts of Sc(OTf)3 yielding tetrahydrothiophene derivatives, products of formal [3 + 2]-cycloaddition reactions, in moderate to high yields. In all studied cases, dimethyl 2-arylcyclopropane dicarboxylates reacted with the corresponding aryl ferrocenyl thioketones in a completely diastereoselective manner to form single products in which (C-2)-Ar and (C-5)-ferrocenyl groups were oriented in a cis-fashion. In contrast, the same cyclopropanes underwent reaction with alkyl ferrocenyl thioketones to form nearly equal amounts of both diastereoisomeric tetrahydrothiophenes. A low selectivity was also observed in the reaction of a 2-phthalimide-derived cyclopropane with ferrocenyl phenyl thioketone.

| S-EPMC7296194 | biostudies-literature

Functional Carbon Materials Derived through Hypergolic Reactions at Ambient Conditions.

Project description:Carbon formation from organic precursors is an energy-consuming process that often requires the heating of a precursor in an oven at elevated temperature. In this paper, we present a conceptually different synthesis pathway for functional carbon materials based on hypergolic mixtures, i.e., mixtures that spontaneously ignite at ambient conditions once its ingredients contact each other. The reactions involved in such mixtures are highly exothermic, giving-off sizeable amounts of energy; hence, no any external heat source is required for carbonization, thus making the whole process more energy-liberating than energy-consuming. The hypergolic mixtures described here contain a combustible organic solid, such as nitrile rubber or a hydrazide derivative, and fuming nitric acid (100% HNO3) as a strong oxidizer. In the case of the nitrile rubber, carbon nanosheets are obtained, whereas in the case of the hydrazide derivative, photoluminescent carbon dots are formed. We also demonstrate that the energy released from these hypergolic reactions can serve as a heat source for the thermal conversion of certain triazine-based precursors into graphitic carbon nitride. Finally, certain aspects of the derived functional carbons in waste removal are also discussed.

| S-EPMC7153381 | biostudies-literature

Regioselective Annulation of 6-Carboxy-Substituted Pyrones as a Two-Carbon Unit in Formal [4 + 2] Cycloaddition Reactions.

Project description:Heterocycles serve as a critical motif in chemistry, but despite being present in more than 85% of pharmaceuticals, there are limited methods for their construction. Here, we describe the incorporation of intact pyrone (2H-pyran-2-one) into larger ring systems via annulation. In a formal [4 + 2] cycloaddition, the pyrone regioselectively accepts a benzylic anion as a nucleophile in a conjugate addition fashion, with the subsequent pyrone-derived enolate attaching to a pendant ester on the initial nucleophile. Subsequent base-driven enolate formation and elimination establish aromaticity of the newly formed ring. After optimization of this process using an NMR-based assessment to overcome solubility and separation challenges, the reaction was successfully applied to a library of 6-ester and -amide-substituted pyrones and using a phenyl ester and other substituted sulfoxides. This technology enables the incorporation of intact pyrone rings into more complex systems, such as for the total synthesis of the natural product thermorubin.

| S-EPMC11232011 | biostudies-literature

Enantiomerically Enriched 1,2-P,N-Bidentate Ferrocenyl Ligands for 1,3-Dipolar Cycloaddition and Transfer Hydrogenation Reactions.

Project description:Novel complexes of 1,2-P,N-bidentate ferrocenyl ligands with AgOAc or with [RuCl?(PPh?)?] as catalysts have been studied in asymmetric synthesis. The catalytic activity of these systems have been studied in [3+2]-cycloaddition of azomethine ylides with olefins and the asymmetric transfer hydrogenation of ketones.

| S-EPMC6100496 | 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