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InCl3/Me3SiCl-catalyzed direct michael addition of enol acetates to alpha,beta-unsaturated ketones

The direct Michael addition of enol acetates to alpha,beta-unsaturated ketones was achieved using a combination of Lewis acid catalysts, InCl 3 and Me3SiCl, which furnished stable enol-form products that could be further transformed into functionalized 1,5-diketones by reactions with various electrophiles.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Organobase catalysed one-pot: Exo -selective synthesis of meso -spiro[cyclohexanone-pyrandione] derivatives

An exo-selective one-pot synthesis of novel spiro[cyclohexanone-pyrandione] derivatives through two sequential organobase-catalysed 1,4-conjugate additions of pyran-2,4-dione precursors on diarylideneacetone derivatives is described. The resulting 7,11-diaryl-2-oxaspiro[5.5]undec-3-ene-1,5,9-triones were obtained as a 2:1 mixture of exo- and endo-diastereomers and adopt a meso-form due to the bilateral symmetry existing in the scaffold. Chiral-HPLC, NMR and single-crystal X-ray diffraction (including synchrotron data) have been used to elucidate the spiro[cyclohexanone-pyrandione] structure, showing therefore the exo/endo-diastereomers obtained in a meso-form, the cis-7,11-diaryl configuration (equatorial position) and different conformational changes in the cyclohexanone skeleton both in liquid and solid states. DFT studies proved the exo-stereoselectivity of the reaction by determining the exo/cis equatorial-equatorial configuration as the most thermodynamically stable form of our spiro[cyclohexanone-pyrandione] skeleton, while the structural substitution has no effect.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Asymmetric iodoamination of chalcones and 4-aryl-4-oxobutenoates catalyzed by a complex based on scandium(III) and a N,N?-dioxide ligand

Highly diastereo- and enantioselective iodoamination of chalcones, 4-aryl-4-oxobutenoates, and a trifluoro-substituted enone has been accomplished in the presence of a chiral N,N?-dioxide/[Sc(OTf)3] complex (0.5-2 mol%), delivering the desired vicinal anti-alpha-iodo-beta-amino carbonyl compounds regioselectively in high yields (up to 97%) and with excellent diastereoselectivities (>99:1 d.r.) and enantioselectivities (up to 99% ee). Enantiopure syn-alpha-iodo-beta-amino products could also be obtained from the isomerization of particular iodo compounds. TsNHX species (X=Cl, Br, I), generated from the reactions between the halo sources and TsNH2, were further confirmed as the active species in the haloamination reactions involved in the formation of the key halonium ion intermediates. A typical haloamination dependency was observed, with reactivity decreasing in the order NBS>NIS?NCS.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

Discovery of (S)-Propane-1,2-diol

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Intermediates for preparing optically active carboxylic acids

A process is described for preparing optically active alpha-arylalkanoic acids consisting of rearranging an optically active ketal of formula STR1 in which the substituents have the meaning given in the description of the invention.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Preparation and Chiroptical Properties of Optically Active Vinyl Ether-Iron and Olefin-Iron Complexes. A CD Quadrant Rule Correlating Absolute Configurations.

Exchange etherification of dicarbonylcyclopentadienyl(eta2-ethyl vinyl ether)iron tetrafluoroborate (4) with optically active primary and secondary alcohols yields a mixture of diastereomeric cations.These isomers are in rapid equilibrium at room temperature.The most favorable equilibrium ratio of such diastereomers (4:1) is achieved with (+)- or (-)-menthol, and the absolute configuration of the predominant diastereomer, formed with (-)-menthol, has been determined.Optically active dicarbonylcyclopentadienyl (eta2-olefin)iron tetrafluoroborate may also be prepared from optically active epoxides.A study of the circular dichroism of these optically active complexes, together with those prepared earlier from the dioxene-iron complex (1), has been carried out and a mechanism by which asymmetry is induced at the achiral metal center is proposed.These observations provide the basis for a quadrant rule relating the sign of the Cotton effect near 450 nm and the absolute configuration of the olefin-iron complex.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Synthesis and biological evaluation of curcumin-like diarylpentanoid analogues for anti-inflammatory, antioxidant and anti-tyrosinase activities

A series of 46 curcumin related diarylpentanoid analogues were synthesized and evaluated for their anti-inflammatory, antioxidant and anti-tyrosinase activities. Among these compounds 2, 13 and 33 exhibited potent NO inhibitory effect on IFN-gamma/LPS-activated RAW 264.7 cells as compared to l-NAME and curcumin. However, these series of diarylpentanoid analogues were not significantly inhibiting NO scavenging, total radical scavenging and tyrosinase enzyme activities. The results revealed that the biological activity of these diarylpentanoid analogues is most likely due to their action mainly upon inflammatory mediator, inducible nitric oxide synthase (iNOS). The present results showed that compounds 2, 13 and 33 might serve as a useful starting point for the design of improved anti-inflammatory agents.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

Extracurricular laboratory:new discovery of 1,5-Diphenylpenta-1,4-dien-3-one

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A stable zerovalent palladium chain enveloped by a pi-electron sheath of conjugated polyene ligands

A surprisingly stable homoleptic Pd04 chain complex of non-activated olefins was isolated and structurally characterized by X-ray crystallographic analysis, and the unique structure and bonding are compared to those of the corresponding dicationic [Pd4]2+ chain sandwich complex. The Royal Society of Chemistry.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Palladium-catalyzed cross-coupling of 2,5-cyclohexadienyl-substituted aryl or vinylic iodides and carbon or heteroatom nucleophiles

2,5-Cyclohexadienyl-substituted aryl or vinylic iodides have been reacted with carbon nucleophiles (diethyl malonate and 2-methyl-1,3- cyclohexanedione), nitrogen nucleophiles (morpholine, potassium phthalimide, N-benzyl tosylamide, di-tert-butyl iminodicarboxylate, lithium azide, and anilines), a sulfur nucleophile (sodium benzenesulfinate), and oxygen nucleophiles (lithium acetate and phenols) to afford products of cyclization and subsequent cross-coupling in good to excellent yields. In most cases, this process is highly diastereoselective. The reaction is believed to proceed via (1) oxidative addition of the aryl or vinylic iodide to Pd(0), (2) organopalladium addition to one of the carbon-carbon double bonds, (3) palladium migration along the carbon chain on the same face of the ring to form a pi-allylpalladium intermediate, and (4) nucleophilic displacement of the palladium.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Novel (R)-2,3-butanediol dehydrogenase, methods for producing same, and methods for producing optically active alcohol using the dehydrogenase

The object of the present invention is to provide an (R)-2,3-butanediol dehydrogenase which uses NADH as a coenzyme, and methods for producing optically active alcohols and ketones using the enzyme. The inventors of the present invention discovered a novel (R)-2,3-butanediol dehydrogenase, isolated a DNA encoding the dehydrogenase, and produced recombinants that express the dehydrogenase at high levels. The dehydrogenase is produced by and can be isolated and purified from Kluyveromyces lactis. The use of the dehydrogenase of the invention enables efficient production of (R)-1,3-butanediol with high optical purity from 4-hydroxy-2-butanone. Also provided by the present invention are methods for efficiently producing (S)-1,3-butanediol with high optical purity from racemic 1,3-butanediol, as well as 4-hydroxy-2-butanone from (R)-1,3-butanediol.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

Brief introduction of (S)-Propane-1,2-diol

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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. HPLC of Formula: C3H8O2, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 4254-15-3, name is (S)-Propane-1,2-diol. In an article£¬Which mentioned a new discovery about 4254-15-3

Triterpenoid saponins from Dianthus chinensis

Four novel triterpenoid saponins, dianchinenosides E, F, G and H have been isolated from the aerial parts of Dianthus chinensis L. Dianchinenosides E and F, G and H are diastereomers with the only difference being in the stereochemistry of the 1,2-propanediol residues esterified to the C-23 of their aglycones. Their structures including the absolute configuration of the 1,2-propanediol fragments were established by spectral and chemical evidence as well as chiral HPLC analysis.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate