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Enantioselective Hydrogenation: V. Hydrogenation of Butane-2,3-dione and of 3-Hydroxybutan-2-one Catalysed by Cinchona-Modified Platinum

Pt/silica modified by cinchonidine and cinchonine is active for the enantioselective hydrogenation of butane-2,3-dione to butane-2,3-diol in dichloromethane at 268-298 K and 10 bar pressure. Reaction proceeds in three stages. In the first, about 85% of the butane-2,3-dione is converted to 3-hydroxybutan-2-one and 15% to three higher molecular weight products by hydrodimerisation. The initial enantiomeric excess in the hydroxybutanone is modest (20 to 40%(R) with cinchonidine as modifier, 10%(S) with cinchonine as modifier) and dependent on the amount of alkaloid used in catalyst preparation. In the second stage, 3-hydroxybutan-2-one is converted to butane-2,3-diol; a marked kinetic effect is observed whereby the minority enantiomer is converted preferentially to butanediol and the enantiomeric excess in the remaining hydroxybutanone increases dramatically to values in the range 62 to 89%(R) and to 30%(S). Under all conditions, the most abundant stereochemical form of the final product is meso-butane-2,3-dione. In the third stage the three dimers are slowly converted by hydrogenation, dissociation, and further hydrogenation to butane-2,3-diol. In the absence of alkaloid, butane-2,3-dione hydrogenation to racemic products in dichloromethane solution proceeds in two distinct stages with no dimer formation. Butane-2,3-dione hydrogenation has also been studied over Pt/silica modified anaerobically by exposure to cinchonidine in ethanol under propyne at 2 bar. This catalyst is remarkably active for the conversion of diketone to diol in ethanol at 293 K and 10 bar and kinetic selection in the second stage of reaction is again observed. The hydrogenation of racemic 3-hydroxybutan-2-one in dichloromethane over cinchonine-modified Pt/silica at 273 K and 10 to 40 bar pressure also showed kinetic selection, an enantiomeric excess of up to 70%(S) appearing in the reactant as it was consumed. Mechanisms which account for these hydrogenations and dimerisations and for the enantioselectivities observed and their variation are presented. This diketone hydrogenation provides an example of consecutive thermodynamic and kinetic control of enantioselectivity in a multistage catalytic reaction.

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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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Reference of 19132-06-0, In homogeneous catalysis, catalysts are in the same phase as the reactants. A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes. 19132-06-0, Name is (2S,3S)-Butane-2,3-diol, molecular formula is C4H10O2. belongs to chiral-oxygen-ligands compounds. In a Patent,once mentioned of 19132-06-0

Hydroxy-substituted antifungals

A compound represented by the formula I STR1 wherein X is independently both F or both Cl or one X is independently F and the other is independently Cl; R1 is a straight or branched chain (C3 to C8) alkyl group substituted by one or two hydroxy moieties, an ether or ester thereof (e.g., a polyether ester, heterocyclic ester amino acid ester or phosphate ester) thereof and the carbon with the asterisk (*) has the R or S absolute configuration or a pharmaceutically acceptable salt thereof and pharmaceutical compositions thereof useful for treating and/or preventing fungal infections are disclosed.

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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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Safe cyano(nitro)methylating reagent – Michael addition of cyano-aci-nitroacetate leading to delta-functionalized alpha-nitronitriles

A practical, convenient, and safe cyano(nitro)methylation method was developed, in which cyano-aci-nitroacetate served as a synthetic equivalent of anionic nitroacetonitrile. A control of the single/double Michael additions was achieved, which enabled the synthesis of unsymmetrical double Michael adducts. Moreover, the Michael adducts can be used as precursors of pyridine and naphthyridine frameworks.

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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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2-Methylene-(20S,25S)-19,27-Dinor-(22E)-Vitamin D Analogs

This invention discloses 2-methylene-(20S,25S)-19,27-dinor-(22E)-vitamin D analogs, and specifically 2-methylene-(20S,25S)-19,27-dinor-(22E)-1alpha,25-dihydroxyvitamin D3, and pharmaceutical uses therefor. This compound exhibits pronounced activity in arresting the proliferation of undifferentiated cells and inducing their differentiation to the monocyte thus evidencing use as an anti-cancer agent and for the treatment of skin diseases such as psoriasis as well as skin conditions such as wrinkles, slack skin, dry skin and insufficient sebum secretion. This compound also has little, if any, calcemic activity and therefore may be used to treat autoimmune disorders or inflammatory diseases in humans as well as renal osteodystrophy. This compound may also be used for the treatment or prevention of obesity.

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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 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:
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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Chiral diphosphinites derived from 2,2-biphosphole as a new class of stereodynamic ligands for enantioselective hydrogenation

New stereodynamic diphosphinites derived from 2,2?-biphosphole, were synthesised by introduction of a linker obtained from chiral diols between the two phosphorus atoms and used for catalytic hydrogenation through a dual chirality control induced by Rh-coordination. The application of these ligands in hydrogenation of dimethyl itaconate shows that the enantioselectivity strongly depends on steric and electronic properties of the chiral linker whereas the sense of enantioselection is determined by the configuration of these stereocentres. These stereodynamic diphosphinites induce higher enantioselectivities than the analogous stereodynamic diphosphanes derived from 2,2-biphosphole. The Royal Society of Chemistry 2009.

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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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Solvent-free and efficient synthesis of highly functionalized cyclohexa-1,3-diene derivatives via a novel one-pot three-component reaction

A catalyst-free and convenient approach for the preparation of cyclohexa-1,3-dienecarboxylate derivatives is described. This three-component reaction between primary amines, alkyl acetoacetate, and dibenzylideneacetone proceeds under solvent-free condition in good to excellent yields. Georg Thieme Verlag Stuttgart.

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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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A novel and efficient stereo-controlled synthesis of hexahydroquinolinones via the diene-transmissive hetero-Diels-Alder reaction of cross-conjugated azatrienes with ketenes and electrophilic dienophiles

The diene-transmissive hetero-Diels-Alder (DTHDA) reactions of cross-conjugated azatrienes (divinylimines or penta-1,4-dien-3-imines) having an N-aryl, N-alkyl, or N-dimethylamino substituent have been examined. The initial reaction of the azatrienes with diphenylketene at room temperature yielded beta-lactams of [2+2] cycloadducts, which upon heating underwent [1,3]-sigmatropic rearrangement to produce the formal [4+2] cycloadducts. The reaction of N-phenylazatriene with dimethylketene or dichloroketene produced the [2+2] cycloadducts only, while the reaction of N-(dimethylamino)azatriene with dichloroketene gave the [4+2] cycloadduct without heating. When the [2+2] cycloadduct has two different vinyl substituents at C-4 of the beta-lactam ring, the regioselectivity of the rearrangement depends on steric factors and the electronic demand of the substituents. The second Diels-Alder reaction of the initial [4+2] cycloadducts with electron-deficient dienophiles (TCNE, N-phenylmaleimide) stereoselectively yielded hexahydroquinolinone derivatives. Similarly, a tandem intermolecular-intramolecular mode of the aza-DTHDA reactions produced tetracyclic nitrogen-containing heterocycles in a regio- and stereoselective manner.

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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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Extractive spectrophotometric determination of trace amounts of copper(II) using 1,5-diphenyl-1,4-pentadien-3-oxime

1,5-Diphenyl-1,4-pentadien-3-oxime (DPPDO) has been identified as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of copper(II). This reagent reacts with copper(II) in the pH range of 2.0-12.0 to form a yellowish-red 1:1 complex in chloroform with a absorbante maximum at 503 nm having molar absorptivity and Sandell’s Sensitivity values of 1.57 × 104 mol-1 cm-1 and 0.004065 mug cm-2 respectively. The developed extractive spectrophotometric method has successfully been employed for the determination of CuII in leafy vegetables etc.

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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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The transformation of simple hydrocarbons into more complex and valuable products via catalytic C–H bond functionalisation has revolutionised modern synthetic chemistry. An article , which mentions HPLC of Formula: C4H10O2, molecular formula is C4H10O2. The compound – (S)-Butane-1,3-diol played an important role in people’s production and life., HPLC of Formula: C4H10O2

A general synthesis of homochiral beta-hydroxy N-acetylcysteamine thioesters

A convenient and efficient route for the enantioselective synthesis of functionalised beta-hydroxy N-acetylcysteamine thioesters is described. The route allows the facile incorporation of vicinal 13C labelling to produce intermediates required for biosynthetic studies on a wide range of polyketide metabolites, e.g. 6-MSA, monocerin, colletodiol and strobilurins.

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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