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One-pot fluorination followed by Michael addition or Robinson annulation for preparation of alpha-fluorinated carbonyl compounds

Fluorination followed by the Michael addition or Robinson annulation of 1,3-dicarbonyl compounds is introduced for the synthesis of acyclic and cyclic alpha-fluoro-beta-ketoesters and alpha-fluoro-1,3-diketones. The decarboxylation step can also be added to the reaction sequence. High efficiency is achieved by the microwave heating and atom economic one-pot synthesis.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Synthesis of 1,5-diaryl-3-arylethenyl-2-pyrazolines under ultrasound irradiation

Synthesis of 1,5-diaryl-3-arylethenyl-2-pyrazolines via the reaction of 1,5-diaryl-1,4-pentadien-3-one and phenyl hydrazine in glacial acetic acid was carried out in 32-80 % yields under ultrasound irradiation. This procedure has the advantages of mild conditions, short reaction time and high yield.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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1,5-bis (2-hydroxyphenyl)pent-1,4-diene-3-one: A lead compound for the development of broad-spectrum antibacterial agents

A systematic and comparative study has been made starting from a naturally-occurring chalcone nucleus to design effective antibacterial agents. The present investigation established 1,5-bis(2-hydroxyphenyl)pent-1,4-diene-3- one (1c) as a lead compound with potential against a panel of pathogenic bacterial strains. Staphylococcus (coagulase negative), Escherichia coli, Pseudomonas aeruginosa, Acenetobacter sp. and Klebsiella pneumoniae. Gentamycine and tetracycline were used as reference drugs. The mode of antibacterial action of Ic was also studied by scanning electron microscopy, which showed membrane disruption and cell lysis of the organisms during the exposure of the tested compound. In vitro toxicity tests demonstrated that all the bioactive compounds showed far less toxicity against human erythrocytes.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Stereoselective oxy-functionalization of gamma-silyl allylic alcohols with ozone: A facile synthesis of silyl peroxide and its reactions

A reaction of gamma-silyl allylic alcohol and its ether with ozone provides synthetically versatile alpha-formyl silyl peroxide in good yield without normal fission of carbon-carbon double bond. Thus, the provided silyl peroxide serves as a good precursor for the stereochemically defined triol derivative via alkylation and reduction of peroxide moiety.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Study of substituent effects in substituted dibenzal acetones

The present work involves a detailed study of the ultra-violet absorption spectra of various substituted dibenzylidene ketones derived from acetone, ethyl methyl ketone, diethyl ketone, cyclopentanone and cyclohexanone by condensing with several meta- and para-substituted benzaldehydes in n-hexane and in ethanol to ascertain the transition dominant in these solvents. These ketones exist as equilibrium mixtures of s-cis, cis and s-cis, trans conformations. The ultraviolet absorption spectra of the ketones exhibit two bands due to pi* ? pi transition around 250 and 320 nm. The 320 nm band is prominent in all the cases. There is no indication of pi* ? n transition in any of the spectra. The 320 nm band is structureless in all the cases except those shown by the dibenzylidene ketones derived from cyclopentanone in hexane. Therefore it can be inferred that the dibenzylide ketones derived from all the ketones except those derived from cyclopentanone are non-planar.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Unexpected bond activations promoted by palladium nanoparticles

Thioether-phosphines, 1 and 2, were applied for the stabilisation of palladium nanoparticles (PdNPs) synthesised by a bottom-up methodology, using [Pd2(dba)3] as an organometallic precursor. For the phenyl containing ligand 1, small (dmean = 1.6 nm), well-defined and dispersed nanoparticles were obtained; however, ligand 2 involving a long alkyl chain led to agglomerates. NMR and GC-MS analyses throughout the synthesis of the nanomaterials revealed partial cleavage of ligands by C-S and C-P bond activations, and XPS spectra of the isolated nanoparticles indicated the presence of both thioether-phosphines and their fragments on the metallic surface. Reactivity studies of molecular palladium systems as well as on extended palladium surfaces pointed out that cluster entities are responsible for C-heteroatom activations, triggering structure modifications of stabilisers during the synthesis of PdNPs. the Partner Organisations 2014.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Organic reactions in subcritical and supercritical water

This review describes applications to several important organic reactions in subcritical and supercritical water.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Stereo- and regioselective photocycloaddition of extended alkenes using gamma-cyclodextrin

Photoexcitation of dibenzalacetones (1a-d) in homogeneous media and solid state yields a mixture of products with poor conversions. Irradiation of the reactants complexed to gamma-cyclodextrin predominantly affords a single dimer (syn adduct 6) despite the possibility for several monomeric and dimeric products. High selectivity in the cavitand-mediated reaction along with the structural characterization of the inclusion complex provides insight into the supramolecular interactions that drive the self-assembly of the host-guest system.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Synthesis of monodisperse oligo(1,4-phenyleneethynylene-alt-1,4- triptycyleneethynylene)s

(Chemical Equation Presented) The synthesis of monodisperse oligo(p-phenyleneethynylene)s 8an with alternating 2,5-dihexyl-1,4-phenylene and 6,14-di-tert-butyl-1,4-triptycylene units and orthogonally protected alkyne end groups is reported. Starting from 6,14-di-tert-butyl-1-(2-triisopropylsilylethynyl)-4-(2-trimethylsilylethynyl) -triptycene (5a), 1,4-dihexyl-2,5-diiodobenzene (10), and 1,4-dihexyl-2-iodo-5- (3-hydroxyprop-1-ynyl)-benzene (9), oligomers with up to four repeating units, i.e., eight phenyleneethynylene units, were prepared through a partially divergent-convergent route with the alkynyl-aryl (Sonogashira-Hagihara) coupling as the key reaction. The starting compound 5a was prepared from triptycenequinone through a sequence of addition of 2- trialkylsilylethynyllithium, reduction and concomitant elimination of water, conversion of the phenol into a triflate, and finally Pd/Cu-catalyzed coupling with trialkylsilylethyne. A similar access to the key compound for a stringent divergent-convergent route, 6,14-di-tert-butyl-1-(3-hydroxybut-1-ynyl)-4-(2- triisopropylsilylethynyl)triptycene (6), is reported. The optical properties of the oligomers 8an and the corresponding oligo(2,5-dihexyl-1,4- phenyleneethynylene) s in dilute solution are almost identical, whereas they differ significantly for the solid, undiluted compounds.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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PYRANDERIVATE DURCH <4+2>-CYCLOADDITION ZWISCHEN alpha,beta-UNGESAETTIGTEN CARBONYLVERBINDUNGEN UND PHOSPHACUMULENYLIDEN

alpha,beta-Unsaturated carbonyl compounds 1 and phosphacumulene ylides 2 undergo a <4+2>-cycloaddition with formation of pyran-substituted phosphoranes 3.Benzoic acid catalyzed Hofmann degradation of 3 yields the deeply coloured pyran derivatives 5.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate