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Room-Temperature Direct beta-Arylation of Thiophenes and Benzo[b]thiophenes and Kinetic Evidence for a Heck-type Pathway

The first example of a regioselective beta-arylation of benzo[b]thiophenes and thiophenes at room temperature with aryl iodides as coupling partners is reported. This methodology stands out for its operational simplicity: no prefunctionalization of either starting material is required, the reaction is insensitive to air and moisture, and it proceeds at room temperature. The mild conditions afford wide functional group tolerance, often with complete regioselectivity and high yields, resulting in a highly efficient catalytic system. Initial mechanistic studies, including 13C and 2H KIEs, suggest that this process occurs via a concerted carbo-palladation across the thiophene double bond, followed by a base-assisted anti-elimination.

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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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Rapid selective defunctionalization of the carbonyl group of alpha,beta-unsaturated ketones with trialkoxylsilane/ZnX2

Reduction of the carbonyl group of ketones to a methylene unit is widely applied in organic syntheses. In this article, we report that trialkoxylsilane/Zn-based catalyst systems may be applied in the reduction of the carbonyl groups of alpha,beta-unsaturated ketones to methylene units under very mild conditions. In comparison with other Zn-based catalysts, excellent rates and high conversions of,-unsaturated ketones to methylene units are obtained using trialkoxylsilane/ZnI2 or ZnCl2. And the same time, the hydrosilylation reaction product could only be detected when using CuI, CuCl, or FeCl3. No reaction could be conducted by using trialkoxylsilane/CoCl2 or NiCl2, in comparison with Zn-based catalysts. Supplemental materials are available for this article. Go to the publisher’s online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. Copyright Taylor &Francis Group, LLC.

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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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gamma-Amino butyric acid analogs as novel potent GABA-AT inhibitors: Molecular docking, synthesis, and biological evaluation

A new series, of gamma-amino butyric acid analogs were designed and synthesized as novel potent GABA-AT inhibitors. A structure-activity relationship study was performed by correlating the effect of different substituents with GABA-AT inhibitory activity of the title compounds. The preliminary bioassays showed that acid hydrazones exhibited excellent inhibitory activities in micromolar (0.07-0.56 muM) range, while Schiff’s bases showed variable results. The most potent compound, 4-amino-N’-[(1Z)-1-(2-bromophenyl) ethylidene]butanehydrazide (AHG177) showed inhibitory potency (IC50) of 0.073 muM. Aminobutyrate transaminase is a pyridoxal-P enzyme which follows a bi-bi ping pong mechanism and in pyridoxamine form can readily transaminate only with succinic semialdehyde and 2-oxoglutarate. The results strongly suggest that only the pyridoxal form of the enzyme is capable of reacting with the ligands. Our findings open up the possibility to extend this protocol to different databases in order to find new potential inhibitor for promising targets based on a rational drug design process.

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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 of alpha, alpha?-bis(substituted benzylidene)ketones catalysed by a SOCl2/EtOH reagent

The cross-aldol condensations of cyclopentanone, cyclohexanone and acetone with benzaldehyde or cinnamaldehyde were catalysed in the presence of SOCl 2, in anhydrous ethanol to synthesise alpha, alpha? -bis(substituted benzylidene) ketones with excellent yields(92-97%).

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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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Syntheses and characterization of polyfunctional organotin chlorides

We report the syntheses and crystal structures of novel organotin chloride complexes with functional organic substituents from HSnCl3¡¤ 2Et2O (1-3). Whereas Cl3SnCHPhCH2C(O)(CH) 2Ph (1) was synthesized in a traditional route from HSnCl 3¡¤2Et2O and dibenzylideneacetone, C 6H5Cl5O4Sn2 (2) and C8H9Cl5O4Sn2 (3) represent products of a condensation reaction of mononuclear organotintrichlorides that comprise both C=C and C=O functional groups and additionally exhibit characteristic intramolecular donor-acceptor interactions. Due to the condensation, compounds 2 and 3 combine SnCl2 with SnCl3 groups within one molecule. Copyright

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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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Debromination of Chalkone Dibromides and Dibenzalacetone Dibromides with Sodium Hydrogen Selenide

Chalkone dibromides (Ia-c) undergo debromination when treated with sodium hydrogen selenide in boiling ethanol to give chalkones (IIa-c).Likewise dibenzalacetone dibromides (IIIa-c) suffer debromination to give dibenzalacetones (IVa-c) which further interact with sodium hydrogen selenide to give 2,4-diaryltetrahydroselenopyran-4-ones (Va-c).

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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

Archives for Chemistry Experiments of 1,5-Diphenylpenta-1,4-dien-3-one

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A novel transition metal-free conjugate reduction of alpha,beta-unsaturated ketones with tosylhydrazine as a hydrogen source

A novel and efficient method has been developed for the chemoselective conjugate reduction of alpha,beta-unsaturated ketones with tosylhydrazine as a hydrogen source to the corresponding saturated ketones in moderate to good yields. The present protocol does not require the use of transition metal, and is efficient being applicable to a wide range of substrates (25 examples).

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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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Fluorination of nonactivated haloarenes via arynes under mild conditions, resulting from further studies toward Ar-F reductive elimination from palladium(II)

Attempted preparation of N,N- and S,S-chelatestabilized arylpalladium fluorides has led to the finding ofarynemediated fluorination of nonactivated haloarenes with Me4NF in DMSO under mild conditions.

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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 of alpha-aryl enaminones through reactions of beta-aryl enones with benzyl azide

Reaction of benzalacetones and dibenzalacetones with benzyl azide promoted by BF3¡¤OEt2 afforded Z and E densely substituted acyclic alpha-aryl enaminones in 21-95% yield. For benzalacetones major Z-isomers were obtained, while E-isomers were the tendency for dibenzalacetones. The synthesis involves domino 1,3-dipolar cycloaddition and 1,2-aryl migration, and is the first metal free practical alternative to the preparation of acyclic alpha-aryl enaminones from commercially available or easily prepared starting materials.

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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 of Isomerically Pure (E)- and (Z)-1,3-Disubstituted 1,3-Dienes

The (E)-dienes 1a – p were prepared in >98percent purity by dehydrative decarboxylation of the corresponding 4,5-unsaturated 3-hydroxycarboxylic acids 3 with dimethylformamide dimethylacetal (11).The (Z)-isomers 6a – m were obtained by stereouncontrolled Wittig reaction of the phosphorane 18 with the aldehydes 7 and subsequent thermolysis of the resulting (E)-/(Z)-diene mixture.Under these conditions 1 was quantitatively converted into its dimer 5, whereas 6 remained unchanged and was readily separated from 5 by vacuum distillation or column chromatography.

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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