Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of Functionally Substituted Bicyclo[4.2.1]nona-2,4-dienes and Bicyclo[4.2.1]nona-2,4,7-trienes by Cobalt(I)-catalyzed [6? + 2?] Cycloaddition of 2-Tropylcyclohexanone.

ABSTRACT: The [6? + 2?] cycloaddition of 2-tropylcyclohexanone to allenes and alkynes was accomplished for the first time using the three-component catalytic system Co(acac)₂(dppe)/Zn/ZnI₂, thus giving previously unknown functionally substituted bicyclo[4.2.1]nona-2,4-dienes and bicyclo[4.2.1]nona-2,4,7-trienes in high yields (70-89%). The structures of the synthesized carbocycles were reliably proved using modern spectral methods and X-ray diffraction. The in vitro cytotoxic activity of the obtained bicyclo[4.2.1]nona-2,4-dienes and bicyclo[4.2.1]nona-2,4,7-trienes against the Jurkat, K562, and U937 tumor cell lines has been studied.

SUBMITTER: Kadikova GN

PROVIDER: S-EPMC7726926 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of Functionally Substituted Bicyclo[4.2.1]nona-2,4-dienes and Bicyclo[4.2.1]nona-2,4,7-trienes by Cobalt(I)-catalyzed [6π + 2π] Cycloaddition of 2-Tropylcyclohexanone.

Kadikova Gulnara N GN Dzhemileva Lilya U LU D'yakonov Vladimir A VA Dzhemilev Usein M UM

ACS omega 20201124 48

The [6π + 2π] cycloaddition of 2-tropylcyclohexanone to allenes and alkynes was accomplished for the first time using the three-component catalytic system Co(acac)2(dppe)/Zn/ZnI2, thus giving previously unknown functionally substituted bicyclo[4.2.1]nona-2,4-dienes and bicyclo[4.2.1]nona-2,4,7-trienes in high yields (70-89%). The structures of the synthesized carbocycles were reliably proved using modern spectral methods and X-ray diffraction. The in vitro cytotoxic ...[more]

PMID: 33324856

Similar Datasets

Synthesis of New Functionally Substituted 9-Azabicyclo[4.2.1]nona-2,4,7-trienes by Cobalt(I)-Catalyzed [6π + 2π]-Cycloaddition of N-Carbocholesteroxyazepine to Alkynes.

Project description:Catalytic [6π + 2π]-cycloaddition of N-carbocholesteroxyazepine with functionally substituted terminal alkynes and 1,4-butynediol was performed for the first time under the action of the Co(acac)2(dppe)/Zn/ZnI2 three-component catalytic system. The reaction gave previously undescribed but promising 9-azabicyclo[4.2.1]nona-2,4,7-trienes (in 79-95% yields), covalently bound to a natural metabolite, cholesterol. The structure of the synthesized azabicycles was confirmed by analysis of one- and two-dimensional (1H, 13C, DEPT 13C, COSY, NOESY, HSQC, HMBC) NMR spectra.

| S-EPMC8156619 | biostudies-literature

Cobalt(I)-Catalyzed [6π + 2π] Cycloaddition of 1,2-Dienes and 1,3-Diynes to N-Carbocholesteroxyazepine in the Synthesis of Previously Undescribed Heterofunctional 9-Azabicyclo[4.2.1]nonadi(tri)enes.

Project description:Promising heterofunctional (E)-9-azabicyclo[4.2.1]nona-2,4-dienes (79-92%) and 9-azabicyclo[4.2.1]nona-2,4,7-trienes (77-90%) containing a cholesterol fragment in the structure have been synthesized for the first time through the [6π + 2π] cycloaddition reaction of terminal 1,2-dienes and symmetric 1,3-diynes with N-carbocholesteroxyazepine under the action of the Co(acac)2(dppe)/Zn/ZnI2 three-component catalytic system.

| S-EPMC8388074 | biostudies-literature

Regiodivergent hydrosilylation, hydrogenation, [2π + 2π]-cycloaddition and C-H borylation using counterion activated earth-abundant metal catalysis.

Project description:The widespread adoption of earth-abundant metal catalysis lags behind that of the second- and third-row transition metals due to the often challenging practical requirements needed to generate the active low oxidation-state catalysts. Here we report the development of a single endogenous activation protocol across five reaction classes using both iron- and cobalt pre-catalysts. This simple catalytic manifold uses commercially available, bench-stable iron- or cobalt tetrafluoroborate salts to perform regiodivergent alkene and alkyne hydrosilylation, 1,3-diene hydrosilylation, hydrogenation, [2π + 2π]-cycloaddition and C-H borylation. The activation protocol proceeds by fluoride dissociation from the counterion, in situ formation of a hydridic activator and generation of a low oxidation-state catalyst.

| S-EPMC6524663 | biostudies-literature

Alkanethiolate-capped palladium nanoparticles for selective catalytic hydrogenation of dienes and trienes.

Project description:Selective hydrogenation of dienes and trienes is an important process in the pharmaceutical and chemical industries. Our group previously reported that the thiosulfate protocol using a sodium S-alkylthiosulfate ligand could generate catalytically active Pd nanoparticles (PdNP) capped with a lower density of alkanethio-late ligands. This homogeneously soluble PdNP catalyst offers several advantages such as little contamination via Pd leaching and easy separation and recycling. In addition, the high activity of PdNP allows the reactions to be completed under mild conditions, at room temperature and atmospheric pressure. Herein, a PdNP catalyst capped with octanethiolate ligands (C8 PdNP) is investigated for the selective hydrogenation of conjugated dienes into monoenes. The strong influence of the thiolate ligands on the chemical and electronic properties of the Pd surface is confirmed by mechanistic studies and highly selective catalysis results. The studies also suggest two major routes for the conjugated diene hydrogenation: the 1,2-addition and 1,4-addition of hydrogen. The selectivity between two mono-hydrogenation products is controlled by the steric interaction of substrates and the thermodynamic stability of products. The catalytic hydrogenation of trienes also results in the almost quantitative formation of mono-hydrogenation products, the isolated dienes, from both ocimene and myrcene.

| S-EPMC5918276 | biostudies-literature

Allene-alkyne cross-coupling for stereoselective synthesis of substituted 1,4-dienes and cross-conjugated trienes.

Project description:Titanium-mediated cross-coupling of allenic alcohols with alkynes has been investigated. Divergent reaction pathways were discovered that provide either stereodefined 1,4-dienes or substituted cross-conjugated trienes. In short, allene substitution plays a critical role in the determination of reaction pathway.

| S-EPMC2577592 | biostudies-literature

Gold(I)-catalyzed enantioselective [4 + 2]-cycloaddition of allene-dienes.

Project description:An enantioselective gold(I)-catalyzed intramolecular [4 + 2]-cycloaddition of allenes and dienes is reported. The reactions allow for the asymmetric synthesis of trans-hexahydroindenes and pyrrolidine products using C(3)-symmetric phosphitegold(I) and ortho-arylphosphoramiditegold(I) complexes as catalysts, respectively.

| S-EPMC2798906 | biostudies-literature

[2+2] cycloaddition of 1,3-dienes by visible light photocatalysis.

Project description:[2+2] photocycloadditions of 1,3-dienes represent a powerful yet synthetically underutilized class of reactions. We report that visible light absorbing transition metal complexes enable the [2+2] cycloaddition of a diverse range of 1,3-dienes. The ability to use long-wavelength visible light is attractive because these reaction conditions tolerate the presence of sensitive functional groups that might be readily decomposed by the high-energy UVC radiation required for direct photoexcitation of 1,3-dienes. The resulting vinylcyclobutane products are poised for a variety of further diversification reactions, and this method is consequently expected to be powerfully enabling in the synthesis of complex organic targets.

| S-EPMC4134740 | biostudies-literature

Asymmetric synthesis of bicyclo[4.3.1]decadienes and bicyclo[3.3.2]decadienes via [6 + 3] trimethylenemethane cycloaddition with tropones.

Project description:The cyanosubstituted trimethylenemethane donor undergoes palladium-catalyzed [6 + 3] cycloaddition with a variety of tropones to yield bicyclo[4.3.1]decadienes in excellent regio-, diastereo-, and enantioselectivity. Products of the Pd-TMM [6 + 3] cycloaddition participate in a thermal [3,3] sigmatropic rearrangement to yield bicyclo[3.3.2]decadienes in good yield.

| S-EPMC2665030 | biostudies-literature

A shape changing tandem Rh(CNC) catalyst: preparation of bicyclo[4.2.0]octa-1,5,7-trienes from terminal aryl alkynes.

Project description:The preparation of a range of tetraaryl-substituted bicyclo[4.2.0]octa-1,5,7-trienes using a one-pot procedure starting from terminal aryl alkynes and catalysed by a rhodium(i) complex is reported. This synthesis proceeds by a reaction sequence involving head-to-tail homocoupling of the terminal alkyne and zipper annulation of the resulting gem-enyne. The rhodium catalyst employed is notable for the incorporation of a flexible NHC-based pincer ligand, which is suggested to interconvert between mer- and fac-coordination modes to fulfil the orthogonal mechanistic demands of the two transformations. Evidence for this interesting auto-tandem action of the catalyst is provided by reactions of the precatalyst with model substrates, corroborating proposed intermediates in both component cycles, and norbornadiene, which reversibly captures the change in pincer ligand coordination mode, along with a DFT-based computational analysis.

| S-EPMC7053420 | biostudies-literature

Concerted Ring Opening and Cycloaddition of Chiral Epoxy Enolsilanes with Dienes.

Project description:Silyl-triflate-catalyzed (4+3) cycloadditions of epoxy enolsilanes with dienes provide a mild and chemoselective synthetic route to seven-membered carbocycles. Epoxy enolsilanes containing a terminal enolsilane and a single stereocenter undergo cycloaddition with almost complete conservation of enantiomeric purity, a finding that argues against the involvement of oxyallyl cation intermediates which have been previously proposed for these types of reactions. Reported are theoretical and experimental investigations of the cycloaddition mechanism. The major enantiomers of the cycloadducts are derived from S(N)2-like reactions of the silylated epoxide with the diene, in which stereospecific ring opening and formation of the two new C-C bonds occur in a single step. Calculations predict, and experiments confirm, that the observed small losses of enantiomeric purity are traced to a triflate-mediated double S(N)2 cycloaddition pathway.

| S-EPMC4527606 | 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