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A protocol for a practical and direct addition of alpha-and gamma-alkyl azaarenes to N-sulfonyl aldimines has been developed. Copper salts act as efficient Lewis acid catalysts for direct Mannich-type reactions providing a mild and fast access to various functionalized heterocycles.(Figure Presented)

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

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The photochemistry of the retinoid analogue A1E shows an oxygen and solvent dependence. Irradiation of A1E with visible right (gamma irr = 425 nm) in methanol solutions resulted in pericyclization to form pyridinium terpenoids. Although the quantum yield for this cyclization is low (?10-4), nevertheless the photochemical transformation occurs with quantitative chemical yield with remarkable chemoselectivity and diastereoselectivity. Conversely, irradiation of A1E under the same irradiation conditions in air-saturated carbon tetrachloride or deuterated chloroform produced a cyclic 5,8-peroxide as the major product. Deuterium solvent effects, experiments utilizing endoperoxide, phosphorescence, and chemiluminescence quenching studies strongly support the involvement of singlet oxygen in the endoperoxide formation. It is proposed that, upon irradiation, in the presence of oxygen, A1E acts as a sensitizer for generation of singlet oxygen from triplet oxygen present in the solution; the singlet oxygen produced reacts with A1E to produce cyclic peroxide. Thus, the photochemistry of A1E is characterized by two competing reactions, cyclization and peroxide formation. The dominant reaction is determined by the concentration of oxygen, the concentration of A1E, and the lifetime of singlet oxygen in the solvent employed. If the lifetime of singlet oxygen in a given solvent is long enough, then oxidation (peroxide formation) is the major reaction. If the singlet oxygen produced is quenched by the protonated solvent molecules faster than singlet oxygen reacts with A1E, then cyclization dominates.

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

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Acid dissociation, as well as cationic homo- and heteroconjugation constants have been determined by potentiometric titration in systems involving substituted pyridines and conjugate cationic acids in the polar protophobic aprotic solvent acetone and in polar amphiprotic methanol. The values of the constant were compared with those previously determined in other polar protophobic aprotic solvents, acetonitrile, nitromethane and propylene carbonate. The pK(a) values of the protonated pyridine derivatives in acetone range between 2.69 and 12.69 and are on average 2-3 orders of magnitude higher than those determined in water. The pK(a) values in methanol vary between 1.02 and 10.37, and are only slightly higher than those in water, the difference not exceeding one order of magnitude. A comparison of the acid dissociation constants determined in all the non-aqueous solvents considered shows that the strength of the cationic acids increases on going from acetonitrile through nitromethane, propylene carbonate and acetone to methanol. In almost all systems of the type: a pyridine derivative its conjugate acid, the cationic homoconjugation equilibrium is present in acetone (1.60SDS of cas: 108-47-4, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 108-47-4, in my other articles.

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

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A family of pincer-ligated cobalt complexes has been synthesized and are active for the catalytic C-H borylation of heterocycles and arenes. The cobalt catalysts operate with high activity and under mild conditions and do not require excess borane reagents. Up to 5000 turnovers for methyl furan-2-carboxylate have been observed at ambient temperature with 0.02 mol % catalyst loadings. A catalytic cycle that relies on a cobalt(I)-(III) redox couple is proposed.

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

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Pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, quinoline, isoquinoline and 2-chloropyridine are readily oxidized to their N-oxides with a solution of trichloroisocyanuric acid, acetic acid, sodium acetate and water in acetonitrile and methylene dichloride in 78%-90% yields.

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

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Alkanolamine based post-combustion capture processes (PCC) are currently the most attractive technologies for CO2 capture. Solvents are degraded in this service by flue gas components, for example oxygen. Solvent degradation can be classified into two reaction types: 1) amine oxidative degradation through a) autoxidation pathways, b) oxidation in the presence of metal ions and 2) thermal degradation including reactions in the presence of CO2. This study represents a literature survey of oxidative degradation (reaction type 1a) of 2-Amino-1-ethanol (MEA), 2-Amino-2-methyl-1- propanol (AMP), N,N-Bis(2-hydroxyethyl)methyl-amine (MDEA), and Piperazine (Pz). Thermal degradation products (reaction type 2) are included where appropriate in order to contribute to a more complete degradation overview of these compounds.

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

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Provided herein are sirtuin-modulating compounds of formula (II) The sirtuin-modulating compounds may be used for increasing the lifespan of a cell, and treating and/or preventing a wide variety of diseases and disorders including, for example, diseases or disorders related to aging or stress, diabetes, obesity, neurodegenerative diseases, cardiovascular disease, blood clotting disorders, inflammation, cancer, and/or flushing as well as diseases or disorders that would benefit from increased mitochondrial activity. Also provided are compositions comprising a sirtuin-modulating compound in combination with another therapeutic agent.

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

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Aqueous 2-amino-2-methyl-1-propanol (AMP) solution and the blends of AMP with other amines appear to be commercially attractive solvents for post-combustion CO2 capture by chemical absorption. To get an understanding of the chemistry of AMP oxidation, oxidative degradation of AMP was investigated in a closed-batch autoclave reactor at 80C and in an open-batch photochemical reactor in the presence of UV radiation at 55C. The degradation products were identified or quantified by ion chromatography (IC) and gas chromatography-mass spectrometry (GC-MS). The effect of temperature on final degradation product distribution was discussed based on the results of thermally accelerated AMP oxidation experiments. The degradation products of AMP oxidation in the presence of UV radiation were compared with that identified in the thermally accelerated AMP oxidation. A summarized scheme for AMP oxidation is proposed to account for the formation of all of the identified products.

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

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A three-component reaction of dimethyltin dibromide with imidazo[1,2-a]pyridine, pyridine derivatives, or isoquinoline and allyl bromide in refluxing ethanol affords the ionic complex, bis(1-allylcycloiminium) dimethyltetrabromostannate (II). The reaction involves N-allylation of cycloimine accompanied by the coordination of two bromide ions with the tin atom of dimethyltin dibromide. The complexes have been characterized by infrared and1H NMR,13C NMR, and119Sn NMR studies. The X-ray crystal structure analysis of a complex reveals the tin atomto be hexacoordinated and the dimethyltetrabromostannate (II) anion having octahedral geometry. Some of the complexes tested for their insecticidal activity are found to exhibit strong activity against Tribolium castaneum insect with LC50ranging from 0.4 to 0.8 ppm.

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

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