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Copper(II)-catalyzed aerobic oxidative coupling between chalcone and 2-aminopyridine via C-H amination: An expedient synthesis of 3-aroylimidazo[1,2-a]pyridines

A simple and efficient protocol has been developed for the synthesis of 3-aroylimidazopyridines via copper(II) acetate-catalyzed aerobic oxidative amination. A library of 3-aroylimidazopyridines was synthesized from readily accessible chalcones and 2-aminopyridines with high yields and regioselectivity. The reaction proceeds through a tandem Michael addition followed by an intramolecular oxidative amination. The successful application of this methodology for a gram-scale reaction indicates its potential for bulk synthesis.

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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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Organocatalytic conjugate addition of malononitrile to conformationally restricted dienones

Organocatalytic conjugate addition of malononitrile to conformationally restricted dienones has been studied. A series of chiral primary and tertiary amine catalysts were screened. A piperidine-based thiourea-tertiary amine was found to be the efficient catalyst. Chiral pyran derivatives were obtained in excellent yields and enantioselectivities via a cascade conjugate addition-intramolecular cyclization pathway. The reaction is remarkably different for the corresponding reaction of conformationally flexible dienones.

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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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Iridium phosphine abnormal N-heterocyclic carbene complexes in catalytic hydrogen transfer reactions

Several iridium complexes bearing chelating abnormal N-heterocyclic carbenes (NHCs) are shown to be active catalysts for transfer hydrogenation of ketones or enones, dehydrative C-C coupling between primary and secondary alcohols, and dehydrogenation of benzyl alcohol to benzyl benzoate. In the transfer hydrogenation of acetophenone, abnormal NHC complexes give higher activity than a normal analogue. Dehydrative C-C coupling reactions between primary and secondary alcohols result in beta-alkylation of the secondary alcohols, using primary alcohols as the apparent alkylating reagents, and such reactions proceed with high yield and selectivity. These catalytic processes are known to involve metal-mediated temporary borrowing of hydrogen from alcohols and subsequent delivery of the hydrogen to CC and /or CO bonds.

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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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Formation of palladium phosphides in the reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus

The reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus was studied using the methods of NMR, UV spectroscopy, and X-ray powder diffraction. The products of the reaction are shown to be palladium phosphides, their composition depending on the ratio of the reagents. The mechanism of the formation of the palladium-enriched phosphides is suggested, which includes the formation of palladium diphosphide PdP2 that subsequently reacts with the excess of bis(dibenzylideneacetone)palladium(0) leading to palladium phosphides Pd5P2, Pd3P0.8, Pd 4.8P, and free dibenzylideneacetone. Pleiades Publishing, Ltd., 2012.

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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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N-Heterocyclic Carbene-Catalyzed Double Michael Addition: Stereoselective Synthesis of Spirofluorenes and Multisubstituted Indanes

The strong Br¡ãnsted basic character of N-heterocyclic carbenes (NHCs) has been used to promote the cascade double Michael addition between fluorenes and dienones. Under catalyst loadings of 1?5 mol% of NHC, fluorene reacts with divinyl ketones (DVKs) to afford anti-spirofluorene compounds in high yields. However, when benzenedi(enones) were employed as Michael acceptors in the presence of 10 mol% of NHC, fluorene undergoes a different inter- and intramolecular cascade double Michael addition, providing multi-substituted indanes in high yields with excellent diastereoselectivity. (Figure presented.).

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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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Bis-chelated palladium(II) complexes with nitrogen-donor chelating ligands are efficient catalyst precursors for the CO/styrene copolymerization reaction

A series of dicationic bis-chelated palladium(II) complexes [Pd(N-N)2][X]2 (N-N = 2,2?-bipyridine (bipy), 1,10-phenanthroline (phen), and their substituted derivatives; X = PF6-, BF4-, OTf-, OTs-) has been synthesized and completely characterized both in the solid state and in solution. The synthetic procedure involves a simple one-pot reaction between Pd(MeCOO)2 and [(N-N)H][X]. These compounds are very active precatalysts for the CO/ styrene copolymerization yielding perfectly alternating polyketones. The crystal structures of some complexes of the series provide evidence that a distorsion from the ideal square planar geometry toward a twist conformation occurs. In DMSO solution, one of the two nitrogen-donor ligands is involved in a dissociative equilibrium yielding a monochelated complex with two cis coordination sites available for the copolymerization catalytic process. The catalytically active species is very stable in 2,2,2-trifluoroethanol, where its activity was found unaltered for at least 48 h of reaction without apparent decomposition to palladium metal. The addition of 1,4-benzoquinone (BQ) to the catalytic system has a strong influence on the yield and, above all, on the molecular weight of polyketones. The zerovalent palladium complexes [Pd(N-N)(BQ)], which might be formed during the copolymerization process, have been synthesized and characterized. The crystal structure of [Pd(bipy)(BQ)] shows that benzoquinone acts as a mono-olefinic ligand to Pd. In the presence of protons, the Pd(0) complexes are readily oxidized to Pd(II) with the reduction of benzoquinone to hydroquinone. When [(N-N)H][X] is used as the source of protons, the resulting Pd(II) species is the precatalyst and can immediately re-enter the catalytic cycle.

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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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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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Kinetic Resolution of beta-Hydroxy Carbonyl Compounds via Enantioselective Dehydration Using a Cation-Binding Catalyst: Facile Access to Enantiopure Chiral Aldols

A practical and highly enantioselective nonenzymatic kinetic resolution of racemic beta-hydroxy carbonyl (aldol) compounds through enantioselective dehydration process was developed using a cation-binding Song’s oligoethylene glycol (oligoEG) catalyst with potassium fluoride (KF) as base. A wide range of racemic aldols was resolved with extremely high selectivity factors (s = up to 2393) under mild reaction conditions. This protocol is easily scalable. It provides an alternative approach for the syntheses of diverse biologically and pharmaceutically relevant chiral aldols in enantiomerically pure form. For example, racemic gingerols could participate in this kinetic resolution with superb efficiency (s > 240), affording both enantiomerically pure gingerols and corresponding shogaols simultaneously in a single step. The dramatic effectiveness of such kinetic resolution process can be ascribed to systematic cooperative hydrogen-bonding catalysis in a densely confined supramolecular chiral cage in situ generated from the chiral catalyst, substrate, and KF.

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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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Derivatives of 2,3-dihydro-1H-1,5-benzodiazepine from o-nitroanilines and chalcones induced by low-valent titanium

2,3-Dihydro-1H-1,5-benzodiazepines have been prepared in good yield by reaction of o-nitroanilines with chalcones induced by the TiCl4-Sm-THF system under mild reaction 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