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Metal coordination by sterically hindered heterocyclic ligands, including 2-vinylpyridine, assessed by investigation of cobaloximes

Structural and 1H NMR data have been obtained for cobaloximes with the bulkiest substituted pyridines reported so far. We have isolated in noncoordinating solvents the complexes CH3Co(DH)2L (methylcobaloxime, where DH = the monoanion of dimethylglyoxime) with L = sterically hindered N-donor ligands: quinoline, 4-CH3quinoline, 2,4-(CH3)2pyridine, and 2-R-pyridine (R = CH3, OCH3, CH2CH3, CH=CH2). We have found that the Co-Nax bond is very long in the structurally characterized complexes. In particular, CH3Co(DH)2(4-CH 3quinoline) has a longer Co-Nax bond (2.193(3) A) than any reported for methylcobaloximes. The main cause of the long bonds is unambiguously identified as the steric bulk of L by the fairly linear relationship found for Co-Nax distance vs CCA (calculated cone angle, CCA, a computed measure of bulk) over an extensive series of methylcobaloximes. The linear relationship improves if L basicity (quantified by pKa) is taken into account. In anhydrous CDCl3 at 25C, all complexes except the 2-aminopyridine adduct exhibit 1H NMR spectra consistent with partial dissociation of L to form the methylcobaloxime dimer. 1H NMR experiments at -20C allowed us to assess qualitatively the relative binding ability of L as follows: 2,4-(CH3)2pyridine > 4-CH3quinoline ? quinoline ? 2-CH3pyridine > 2-CH3Opyridine > 2-CH3CH2pyridine > 2-CH2=CHpyridine. The broadness of the 1H NMR signals at 25C suggests a similar order for the ligand exchange rate. The lack of dissociation by 2-aminopyridine is attributed to an intramolecular hydrogen bond between the NH2 group and an oxime O atom. The weaker than expected binding of 2-vinylpyridine relative to the Co-Nax bond length is attributed to rotation of the 2-vinyl group required for this bulky ligand to bind to the metal center, a conclusion supported by pronounced changes in 2-vinylpyridine signals upon coordination.

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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

Simple exploration of 2,4-Dimethylpyridine

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Viscosities of Benzene or Cyclohexane +2,4-Lutidine, +2,6-Lutidine, +Collidine, +Mesitylene, +m-Xylene, and +p-Xylene, at 303.15, 313.15 and 323.15 K

Densities and viscosities of the binary mixtures (benzene or cyclohexane +2,4-lutidine, +2,6-lutidine, +collidine, +mesitylene, +m-xylene and +p-xylene) between 303.15 and 323.15 K over the whole range composition, were determined.Experimental results were fitted to the Grundberg and Nissan equation.The values obtained for the excess viscosities and the parameter delta of the Grundberg-Nissan equation can be explained in terms of the dipole moments of the compounds, the ?-electron structure of the aromatic molecules and the formation of electron donor-acceptor complexes.

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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

The important role of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Catalytic aerobic oxidation of alcohols by Fe(NO3)3-FeBr3

Selective aerobic oxidation of secondary and benzylic alcohols was efficiently accomplished by the binary catalyst system Fe(NO3)3-FeBr3 under air at room temperature. The oxidation developed in mild conditions and showed good yields. A secondary alcohol even in the presence of a primary one was selectively oxidized.

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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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Modification of the pyridine moiety of non-peptidyl indole GnRH receptor antagonists.

The synthesis of a number of indole GnRH antagonists is described. Oxidation of the pyridine ring nitrogen, combined with alkylation at the two position, led to a compound with an excellent in vitro activity profile as well as oral bioavailability in both rats and dogs.

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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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Synthetic Route of 126456-43-7, A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 126456-43-7, Name is (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, molecular formula is C9H11NO. In a Article£¬once mentioned of 126456-43-7

Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels

We describe the self-assembly properties of chiral N,N?-disubstituted urea-based organocatalyst 1 that leads to the formation of hierarchical supramolecular gels in organic solvents at low concentrations. The major driving forces for the gelation are hydrogen bonding and pi-pi interactions according to FTIR and 1H NMR spectroscopy, as well as quantum-mechanical studies. The gelation scope could be interpreted based on Kamlet-Taft solvatochromic parameters. TEM, SEM, and AFM imaging revealed that a variety of morphologies including helical, laths, porous, and lamellar nanostructures could be obtained by varying the solvent. Experimental gelation tests and computational structural analysis of various structurally related compounds proved the existence of a unique set of molecular interactions and an optimal hydrophilic/hydrophobic balance in 1 that drive the formation of stable gels. Responses to thermal, mechanical, optical, and chemical stimuli, as well as multifunctionality were demonstrated in some model gel materials. Specifically, 1 could be used for the phase-selective gelation of organic solvent/water mixtures. The gel prepared in glycerol was found to be thixotropic and provided a sensitive colorimetric method for the detection of Ag I ions at millimolar concentrations in aqueous solution. Moreover, the gel matrix obtained in toluene served as a nanoreactor for the Friedel-Crafts alkylation of 1H-indole with trans-beta-nitrostyrene. Multifunctional gels: Urea-based organocatalyst 1 undergoes hierarchical self-assembly in organic solvents that leads to the formation of stable organogels. These materials show multistimuli responsive behaviors and multifunctional properties, including phase-selective gelation of organic solvent/water mixtures, colorimetric sensing of silver ions at millimolar concentrations, and operation as a nanoreactor for indole alkylation (see scheme).

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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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Related Products of 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£¬once mentioned of 108-47-4

PYRIDINES. XIV – ACYLATION DE PYRIDYL-LITHIOENAMIDINES. SYNTHESE DE PYRIDYL-N-ACYLENAMIDINES ET DE PYRIDYLPYRIMIDONES-4.

The mixture of PhLi:di- or tri-methylpyridine 1:PhCN:RCOCl (R = Me, Ph, EtO, Me2N) or PHCO2Me (molar ratio 3:1:3:3) leads through the intermediates primary lithioenamines 3 and lithioenamidines 4, to acylated products, N-acylenamines (enamides) 5, beta-diketones and beta-ketoesters 6, C-acylenamides 7, N-acyleneamidines 8 and their cyclization derivatives, pyridylhydroxypyrimidines 10 (yield up to 60 percent) and pyridyldihydropyrimidones 11 (yield up to 10 percent).Distillation of the crude extract leads to naphthyridones 12 (yield up to 10 percent) which result from thermocyclization of the enamides 5f, 5g and 7f.Various by-products are isolated such as N,N-dimethyl-N’,N’-diphenylmethyleneurea resulting from N-lithiodiphenylketimine and phenacylpyridines 13.Crotonization and oxidation of the latter compounds lead to the aza-analogues 14, 15 of dibenzoylstilbenes.

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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

A new application about (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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PROCESS FOR THE DE-ENRICHMENT OF ENANTIOMERICALLY ENRICHED SUBSTRATES

There is provided a process for the de-enrichment of enantiomerically enrichedcompositions which comprises reacting an enantiomerically enriched compositioncomprising at least a first enantiomer or diastereomer of a substrate comprisinga carbon-heteroatom bond, wherein the carbon is a chiral centre and the heteroatomis a group VI heteroatom, in the presence of a catalyst system and optionally areaction promoter to give a product composition comprising first and secondenantiomers or diastereomers of the substrate having a carbon-heteroatom bond,the ratio of second to first enantiomer or disatereomer in the product compositionbeing greater than the ratio of second to first enantiomer or disatereomer inthe enantiomerically enriched composition. Preferred substrates includecompounds of Formula (1) wherein: X represents O, S; R1, R2each independently represents an optionally substituted hydrocarbyl, a perhalogenatedhydrocarbyl, an optionally substituted heterocyclyl group; or R1& R2 are optionally linked in such a way as to form an optionallysubstituted ring(s); provided that R1 and R2are selectedsuch that * is a chiral centre. In a preferred process a compound of Formula : (2)wherein: X represents O, S; R1, R2 each independently representsan optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl, an optionallysubstituted heterocyclyl group; or R1 & R2 are optionallylinked in such a way as to form an optionally substituted ring(s); provided thatR1 and R2 are different, may be obtained.

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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

Archives for Chemistry Experiments of 2,4-Dimethylpyridine

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SUBSTITUTED 7-AZA[2.2.1]BICYCLOHEPTANES FOR THE TREATMENT OF DISEASE

The invention provides compounds of Formula I: which may be in the form of pharmaceutical acceptable salts or compositions, are useful in treating diseases or conditions in which alpha7 nicotinic acetylcholine receptors (nAChRs) are known to be involved.

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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

Simple exploration of 2,4-Dimethylpyridine

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A novel and practical synthesis of 3-unsubstituted indolizines

A novel and practical procedure for the preparation of 3-unsubstituted indolizines by 1,3-dipolar cycloaddition was developed. The requisite pyridinium N-methylides were generated simply from the corresponding N-(carboxymethyl)pyridinium halides. In the presence of MnO2, electron-deficient alkenes, instead of alkynes or vinyl bromides, were used successfully as dipolarophiles. This general method features cheap reagents, simple workup procedure and gives the products in moderate to high yields (57-92%).

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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

Archives for Chemistry Experiments of 108-47-4

The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 108-47-4 is helpful to your research. Application of 108-47-4

Application of 108-47-4, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 108-47-4, molcular formula is C7H9N, introducing its new discovery.

Factors Dictating the Nuclearity/Aggregation and Acetate Coordination Modes of Lutidine-Coordinated Zinc(II) Acetate Complexes

The reactions of Zn(OAc)2¡¤2H2O with various positional isomers of lutidine were explored with a view to understand the factors responsible for the nuclearity/aggregation and acetate coordination modes of the products. The reactions of Zn(OAc)2-2H2O with 3,5-lutldine, 2,3-lutidlne, 2,4-lutidine, and 3,4-lutidine in a 1:1 ratio in methanol at ambient temperature afforded three discrete trlnuclear complexes [Zn 3(OAc)2(mu2-eta2: eta1-OAc)2(mu2 eta1 :eta1-OAc)2(H2O)2(3,5lutidine) 2] (1), [Zn3(mu2-eta1 :eta1-OAC)4(mu2-eta2: eta0-OAC)2L2] [L = 2,3-lutidine (2) and 2,4-lutidine (3)], and a onedimensional coordination polymer [Zn(OAc)(mu2 eta1:eta1-OAc)(3,4-lutidine) ] (4) in 93, 79, 81, and 94% yields, respectively. Complexes 1-4 were characterized by microanalytical, IR, solution (1H and 13C), and solid-state cross-polarization magic angle spinning 13C NMR spectroscopic techniques and single-crystal X-ray diffraction data. Complex 1 is unique In that it contains three types of acetate coordination modes, namely, monodentate, bridging bidentate, and asymmetric chelating bridging. Variable-temperature 1H NMR data indicated that complex 1 partially dissociates In solution, and the remaining undissociated 1 undergoes a rapid “carboxylate shift” even at 218 K. The plausible mechanism of formation of complexes 1 -4 was explained with the aid of a point zero charge (pzc) model, according to which the nuclearity/aggregation observed In complexes 1-4 depends upon the number and nature of equilibrating species formed upon dissolution of the reactants In methanol, and these In turn depend upon the subtle basic/steric properties of lutidines. Further, noncovalent Interactions play a crucial role In determining the nuclearity/ aggregation and acetate coordination modes of the products.

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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