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Cationic (fluoromesityl)palladium(II) complexes

Halide abstraction from [Pd(mu-Cl)(Fmes)(NCMe)]2 (Fmes = 2,4,6-tris(trifluoromethyl)phenyl or nonafluoromesityl) with TlBF4 in CH2Cl2/MeCN gives [Pd(Fmes)(NCMe)3]BF4, which reacts with monodentate ligands to give the monosubstituted products trans-[Pd(Fmes)L(NCMe)2]BF4 (L = PPh3, P(o-Tol)3, 3,5-lut, 2,4-lut, 2,6-lut; lut = dimethylpyridine), the disubstituted products trans-[Pd(Fmes)(NCMe)(PPh3)2]BF4, cis-[Pd(Fmes)(3,5-lut)2(NCMe)]BF4, or the trisubstituted products [Pd(Fmes)L3]BF4 (L = CNtBu, PHPh2, 3,5-lut, 2,4-lut). Similar reactions using bidentate chelating ligands give [Pd(Fmes)(L-L)(NCMe)]BF4 (L-L = bipy, tmeda, dppe, OPPhPy2-N,N?, (OH)(CH3)CPy2-N,N?). The complexes trans-[Pd(Fmes)L2(NCMe)]BF4 (L = PPh3, tht) (tht = tetrahydrothiophene) and [Pd(Fmes)(L-L)(NCMe)]BF4 (L-L = bipy, tmeda) were obtained by halide extraction with TlBF4 in CH2Cl2/MeCN from the corresponding neutral halogeno complexes trans-[Pd(Fmes)ClL2] or [Pd(Fmes)Cl(L-L)]. The aqua complex trans-[Pd(Fmes)(OH2)(tht)2]BF4 was isolated from the corresponding acetonitrile complex. Overall, the experimental results on these substitution reactions involving bulky ligands suggest that thermodynamic and kinetic steric effects can prevail affording products or intermediates different from those expected on purely electronic considerations. Thus,water, whether added on purpose or adventitious in the solvent, frequently replaces in part other better donor ligands, suggesting that the smaller congestion with water compensates for the smaller M-OH2 bond energy.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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POTENTIOMETRIC STUDIES ON COMPLEXES OF SILVER(I) IN SOLUTIONS. PART V. RELATIONSHIP BETWEEN STABILITY CONSTANTS OF Ag(I) COMPLEXES OF PYRIDINE DERIVATIVES AND HAMMET’S ? COEFFICIENTS

By means of the potentiometric method, the processes of formation of Ag(I) complexes of 3-acetyl-, 3-hydroxymethyl-, 2-ethyl-, 2,4-dimethyl-, 2,4,6-trimethyl-, 2-amino-5-methyl-, and 2-amino-4-methylpyridines have been examined in aqueous solutions (I = 0.5 (KNO3), t = 25 deg C).Correlation has been found between pKa and stability coefficient Sf and substituent constants ? for 19 Ag(I) compounds with 3- and 4-substituted pyridine derivatives.Positive value of the slope of Sf = f(?) straight line dependence evidences that the contribution of ?M -> L bond in the metal-ligand co-ordination bond is considerable.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Stereoselective [2,3]-Wittig rearrangement of (1S,2R)-1-amino-indan-2-ol derived amide enolates

An efficient, diastereoselective [2,3]-Wittig rearrangement of alpha-allyloxyamide enolates has been developed using (1S,2R)-1-amino-indan-2-ol as a chiral auxiliary. After auxiliary removal, the resultant optically active a-hydroxy acids have been transformed to functionalized amino acid derivatives.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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108-47-4, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.108-47-4, Name is 2,4-Dimethylpyridine, molecular formula is C7H9N. In a Article, authors is Smith£¬once mentioned of 108-47-4

The relative toxicity of compounds in mainstream cigarette smoke condensate

Many different in vivo and in vitro tests are currently used to assess the toxicity of chemicals and complex mixtures such as cigarette smoke condensate. In vivo tests include assays in rodents to determine carcinogenicity, tumorigenicity and reproductive effects. In vitro tests of mutagenicity are conducted with both bacterial and mammalian cell systems. A first step towards lowering the toxicity of cigarette smoke condensate is the identification of the relevant compounds. However, changing the concentration of a given smoke component may not linearly alter the biological activity of the complex mixture due to interactive effects. The ‘effective toxicity’ of a chemical constituent is a function of the concentration, the metabolic fate, the potency in in vivo and in vitro assays, and the ability to reach the target tissues. The logarithm of the octanol-water partition coefficient (log P) is an important parameter since it affects metabolism, biological transport properties and intrinsic toxicity. Using concentration data from the International Agency for Cancer Research (IARC), biological activity data from the Registry of Toxic Effects of Chemical Substances (RTECS) database and measured and calculated log P values, we have rank ordered some of the important compounds in cigarette smoke condensate by their measured or potential toxicity. Condensates from different cigarette brands, tar categories and styles vary in their concentrations of these compounds. Chemicals of greater commercial or scientific interest may be toxicity tested more extensively, thereby increasing the probability of positive test results and highlighting the need for consideration of structure-activity relationships. Copyright (C) 2000 Elsevier Science Ltd.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Can You Really Do Chemisty Experiments About 2,4-Dimethylpyridine

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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. 108-47-4, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 108-47-4, name is 2,4-Dimethylpyridine. In an article£¬Which mentioned a new discovery about 108-47-4

Synthesis and structure-activity relationship of 7-(substituted)-aminomethyl-4-quinolone-3-carboxylic acid derivatives

Gram-positive organisms have re-emerged as the major hospital pathogens, which make the unmet medical needs for antibacterial therapy even worse. In searching for potent agents against Gram-positive pathogens, novel 7-(substituted)-aminomethyl-quinolone-3-carboxylic acids were designed, synthesized, and evaluated for their antibacterial activities in vitro. Many 7-monoarylaminomethyl derivatives exhibited high potency against Gram-positive organisms compared to reference agents: vancomycin and pazufloxacin. Additionally, a few 7-monoalkylaminomethyl derivatives exhibited good activities against both Gram-positive and Gram-negative organisms.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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108-47-4, In heterogeneous catalysis, the catalyst is in a different phase from the reactants. At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 108-47-4, name is 2,4-Dimethylpyridine. In an article£¬Which mentioned a new discovery about 108-47-4

Asymmetrical synthesis of fluorinated 2-(pyridin-2-yl) alkylamine from fluoromethyl sulfinyl imines and 2-alkylpyridines

A novel strategy was developed to synthesize fluorinated 2-(pyridin-2-yl) alkylamines via condensation of 2-alkylpyridines and chiral fluoromethyl N-tert-butyl sulfinyl imines with good diastereo-control and good chemical yields. The chiral N-tert-butyl sulfinyl auxiliary can be easily removed under mild acidic condition at room temperature. The application of this strategy was demonstrated in the synthesis of a fluorine-containing pesticide candidate.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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108-47-4, Name is 2,4-Dimethylpyridine, belongs to chiral-nitrogen-ligands compound, is a common compound. 108-47-4In an article, authors is Bakhtin, once mentioned the new application about 108-47-4.

Are amines basic or nucleophilic catalysts for oxirane ring opening by proton-donating nucleophiles?

The behavior of amines as catalysts for oxirane acidolysis and phenolysis has been studied using kinetic methods. The apparent catalytic and noncatalytic reaction rate constants have been estimated. It has been demonstrated that the noncatalytic pathway has almost no effect on the apparent reaction rate constant. In order to determine the character of the behavior of amines (bases/nucleophiles) in this reaction, their reactivity has been analyzed within the conceptions of basic and nucleophilic mechanisms of catalysis. Based on the quantitative amine structure – catalytic activity correlation, it has been shown by comparing the values of correlation coefficients (r) of equations describing mechanisms for various reaction systems that, in the reactions of oxiranes with proton donors (carboxylic acids and phenols), the catalytic activity of tertiary amines/pyridines is determined by their nucleophilicity rather than basicity.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Article, the author is Gao, Yaojun and a compound is mentioned, 126456-43-7, (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, introducing its new discovery. 126456-43-7

Enantioselective heterocyclic synthesis of spiro chromanone-thiochroman complexes catalyzed by a bifunctional indane catalyst

Novel asymmetric domino reactions of benzylidenechroman-4-ones and 2-mercaptobenzaldehydes for efficient construction of spiro chromanone- thiochroman complexes were accomplished with high yields and excellent selectivities via a novel bifunctional indane catalyst.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Article, the author is Fu, Yong and a compound is mentioned, 108-47-4, 2,4-Dimethylpyridine, introducing its new discovery. 108-47-4

A novel pyrazole-containing indolizine derivative suppresses NF-kappaB activation and protects against TNBS-induced colitis via a PPAR-gamma-dependent pathway

The nuclear factor-kappaB (NF-kappaB)-mediated activation of macrophages plays a key role in mucosal immune responses in Crohn’s disease (CD). Moreover, increasing evidence shows that the activation of peroxisome proliferator-activated receptor-gamma (PPAR-gamma) exerts satisfactory anti-inflammatory effects in experimental colitis models, mostly by suppressing NF-kappaB-mediated macrophage activation. Therefore, exploring therapeutic strategies to activate PPAR-gamma and inhibit the NF-kappaB pathway in colonic macrophages holds great promise for the treatment of CD. In this study, five novel pyrazole-containing indolizine derivatives (B1, B2, B3, B4 and B5) were successfully synthesized and characterized, and their anti-inflammatory activities for CD treatment were also investigated. Among the five compounds, compound B4 effectively decreased the NF-kappaB-mediated production of the pro-inflammatory cytokine TNF-alpha in LPS-stimulated peritoneal macrophages. Moreover, compound B4 significantly ameliorated 2,4,6-trinitrobenzene sulfonic acid (TNBS)-induced mouse colitis symptoms, including body weight loss, colonic pathological damage and inflammatory cell infiltration. The results of western blotting and luciferase reporter assays indicated that compound B4 activated PPAR-gamma and subsequently suppressed NF-kappaB activation. Conversely, the addition of the PPAR-gamma antagonist GW9662 abrogated the anti-inflammatory effects of compound B4 both in vitro and in vivo. In summary, compound B4 activated the PPAR-gamma pathway to inhibit downstream NF-kappaB signaling, which alleviated experimental colitis. Thus, this compound may serve as a potential therapeutic agent for patients with CD.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Reductive amination process

A process of reductive amination efficiently yields an HIV protease inhibitor.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis