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SYNTHESIS OF SOME 5H-PYRANO- AND 5H-PYRIDO<2',3':4,5>PYRIDO<2,1-b>BENZOTHIAZOL-5-ONE DERIVATIVES

The addition reactions of 3-hydroxy-1H-pyrido<2,1-b>benzothiazol-1-one, 1, have been investigated.Thus, 1 added to aryl isocyanates to give the 2-carbamoyl derivatives 2a,b and to activated alkenes to give the 2-alkylated derivatives 5a-c.Compound 1 reacted also with alpha-substituted cinnamonitriles, 6a-l, to give different products 7, 12, 13 and 15 according to the nature of the substituent in 6.Compounds with the ring systems pyrido<2',3':4,5>pyrido<2,1-b>benzothiazole and pyrano<2',3':4,5>pyrido<2,1-b>benzothiazole have been obtained.The first ring system is a new one.

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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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Nature of the modifying action of white phosphorus on the properties of nanosized hydrogenation catalysts based on bis(dibenzylideneacetone)palladium(0)

The catalytic properties and nature of the nanoparticles forming in the system based on Pd(dba)2 and white phosphorus are reported. A schematic mechanism is suggested for the formation of nanosized palladium-based hydrogenation catalysts. The mechanism includes the formation of palladium nanoclusters via the interaction of Pd(dba)2 with the solvent (N,N-dimethylformamide) and substrate and the formation of palladium phosphide nanoparticles. The inhibiting effect exerted by elemental phosphorus on the catalytic process is due to the conversion of part of the Pd(0) into palladium phosphides, which are inactive in hydrogenation under mild conditions, and the formation of mainly segregated palladium nanoclusters and palladium phosphide nanoparticles. By investigating the interaction between Pd(dba)2 and white phosphorus in benzene, it has been established that the formation of palladium phosphides under mild conditions consists of the following consecutive steps: Pd(0) ? PdP2 ? Pd5P2 ? Pd3P. It is explained why white phosphorus can produce diametrically opposite effects of on the catalytic properties of nanosized palladium-based hydrogenation catalysts, depending on the nature of the palladium precursor.

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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 catalytic alcohol oxidation and ketone transfer hydrogenation activity of donor-functionalized mesoionic triazolylidene ruthenium(ii) complexes

We report on the synthesis of a variety of C,E-bidentate triazolylidene ruthenium complexes that comprise different donor substituents E (E = C: phenyl anion; E = O: carboxylate, alkoxide; E = N: pyridine at heterocyclic carbon or nitrogen). Introduction of these donor functionalities is greatly facilitated by the synthetic versatility of triazoles, and their facile preparation routes. Five different complexes featuring a C,E-coordinated ruthenium center with chloride/cymene spectator ligands and three analogous solvento complexes with MeCN spectator ligands were prepared and evaluated as catalyst precursors for direct base- and oxidant-free alcohol dehydrogenation, and for transfer hydrogenation using basic iPrOH as a source of dihydrogen. In both catalytic reactions, the neutral/mono-cationic complexes with chloride/cymene spectator ligands performed better than the solvento ruthenium complexes. The donor functionality had a further profound impact on catalytic activity. For alcohol dehydrogenation, the C,C-bidentate phenyl-triazolylidene ligand induced highest conversions, while carboxylate or pyridine donor sites gave only moderate activity or none at all. In contrast, transfer hydrogenation is most efficient when a pyridyl donor group is linked to the triazolylidene via the heterocyclic carbon atom, providing turnover frequencies as high as 1400 h-1 for cyclohexanone transfer hydrogenation. The role of the donor group is discussed in mechanistic terms.

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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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Gem-Dimethyl-cyclo-propanation of dibenzyl-ideneacetone using triisopropyl sulfoxonium tetra-fluoro-borate

The reaction between dibenzyl-ideneacetone (dba) and tri-isopropyl sulfoxonium tetra-fluoro-borate has been reinvestigated. The stereochemistry of the major diasteromeric bis-(gem-dimethyl-cyclo-propane) adduct has now been assigned as [(1RS,3RS)-2,2-dimethyl-3-phenyl-cyclo-prop-yl][(1SR,3SR)-2,2- dimethyl-3-phenyl-cyclo-prop-yl]methanone, C23H26O, by X-ray crystallographic studies on a twinned crystal. The asymmetric unit contains two ml-ecules of the adduct, the conformations of which differ in the orientation of the phenyl ring relative to the adjacent cyclo-propanated double bond. The carbonyl groups of each adduct are aligned approximately along the a axis and in opposite directions to each other. The mol-ecules pack to give a sinusoidal pattern along the b axis. This is the first acyclic bis-(dimethyl-cyclo-prop-yl) ketone for which an X-ray crystal structure determination has been reported, and is also the first bis-cyclo-propanated dba analogue. The knowledge that the major diastereomer has the meso structure (and therefore the confirmation that the minor isomer is the racemate) will prove invaluable in future studies to utilize bis-(dimethyl-cyclo-prop-yl) ketones as reagents, in rearrangement processes, and as potential ligands and ligand precursors in organometallic 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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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£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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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£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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Mild hydrosulfenylation of Olefins under neutral conditions using a defined NHC-ligated iron-sulfur catalyst

A defined NHC-Fe-S complex proved to be an efficient catalyst for the selective hydrosulfenylation of alpha,beta-unsaturated ketones or vinylnitriles. A wide range of different aliphatic thiols were transferred in this atom-economic reaction into the corresponding thioethers. Mild reaction conditions, equimolar amounts of substrates, low catalyst loadings, and mild reaction conditions are characteristic for this transformation.

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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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Reversible cleavage of the C-H bond of aldimine with platinum complexes

The reversible cleavage of the C-H bond of aldimine with platinum complexes was studied. For the C-H oxidative addition to occur a heteroatom capable of coordinating to the metal center was necessary in the aldimine molecule. Systematic examinations on the thermodynamics and kinetics of both C-H bond oxidative addition and reductive elimination and catalytic application were 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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NEW ASPECTS OF THE CHEMISTRY OF 2,3-DIHYDRO-1H-1,5-BENZODIAZEPINE

Under basic catalysis conditions the reaction of 4- and 4′-substituted chalcones with o-phenylenediamine leads to 2,3-dihydro-2,4-diaryl-1H-1,5-benzodiazepines; beta-amino adducts, the ability of which to undergo intramolecular condensation increases as the basicity of the catalyst is increased, are formed as intermediates.A different pathway for the process (the formation of an azomethine) is observed in the reaction with cinnamaldehyde.It is concluded that conformational factors play a primary role in the direction of the reaction.

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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