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Rapid entry into the cryptophycin core via an acyl-beta-lactam macrolactonization: total synthesis of cryptophycin-24.

[see structure]. An efficient, concise approach to the macrolide core of the cryptophycins, potent antimitotic agents, has been achieved. The reaction sequence features a novel macrolactonization utilizing a reactive acyl-beta-lactam intermediate that incorporates the beta-amino acid moiety within the 16-membered macrolide core. This highly modular approach, which allows for multiple alterations throughout the structure, was successfully applied to the total synthesis of cryptophycin-24.

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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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Lewis acid/base adducts of TiCl4 and methylpyridines

By the reaction of 2-methyl-and 2,6-dimethylpyridine the first neutral TiCl4L complexes (L = single bonded ligand) could be synthesized. The structures have been determined by single crystal X-ray methods. The best description of the molecular structure is a distorted trigonal bipyramid with the nitrogen base occupying an equatorial position. With 2,4-dimethylpyridine, a 1:2 adduct is formed, where the nitrogen bases are in frans-positions of a TiCl4N2-octahedron, as also confirmed by an X-ray analysis.

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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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Pyridines; XV. Synthesis of Enamides by Selective N-Acylation of Silylated Primary Enamines; Results of the Regioselective Metallation of s-Collidine, 2,4-Lutidine and 2,4-Dimethylquinoline

Nineteen substituted enamides 4 are easily prepared (yields 30-71percent) in chloroform by condensation of various acyl chlorides R4-COCl with the N-trimethylsilylenamines 3.The compounds 3 are obtained from the regioselective N-silylation (yields 60-98percent) of the lithioenamines 2, which result from the condensation of nitriles R3-CN having no alpha-hydrogen atom with 2-lithiomethyl derivatives of s-collidine, 2,4-lutidine and 2,4-dimethylquinoline.

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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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An Improved Liquid-Phase Synthesis of Simle Alkylpyridines

The synthesis of pyridines from mixtures of aldehydes or ketones and NH3 in the liquid phase has been reinvestigated, using continuous dosage of the carbonyl components to the reaction mixture.The main product from the reaction of acetaldehyde and formaldehyde is 3-methylpyridine (6), which is also the main product from the reaction of acrolein or a mixture of crotonaldehyde and formaldehyde under the same conditions.The reaction of other aldehydes with formaldehyde give 3,5-dialkylpyridines, e.g. 10, 16.Acetone reacts with either formaldehyde or acetaldehyde to give polysubstituted alkylpyridines.A mechanistic pathway is proposed which accounts for the formation of the observed 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

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Prolinamide bridged silsesquioxane as an efficient, eco-compatible and recyclable chiral organocatalyst

A new organic-inorganic hybrid silica material derived from a bis-silylated prolinamide by sol-gel methodology has been successfully applied as a supported organocatalyst in asymmetric aldol and Michael reactions. Our immobilized system presents similar performances to homogeneous prolinamides and added advantages of easy recovery and good recyclability. It fits green chemistry requirements as the reactions are performed in water, at room temperature, with low catalyst loadings (2-16 mol%).

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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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IMIDAZOPYRIDINE AND RELATED ANALOGS AS SIRTUIN MODULATORS

Provided herein are novel sirtuin-modulating compounds and methods of use thereof. 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£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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MONO QUATERNARY AMMONIUM SALTS AND METHODS FOR MODULATING NEURONAL NICOTINIC ACETYLCHOLINE RECEPTORS

Provided are monoquaternary ammonium compounds which are modulators of nicotinic acetylcholine receptors. Also provided are methods of using the compounds for modulating the function of a nicotinic acetylcholine receptor, and for the prevention and/or treatment of central nervous system disorders, substance use and/or abuse, and or gastrointestinal tract disorders.

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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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Continuous two-step catalytic conversion of glycerol to pyridine bases in high yield

Glycerol was converted to pyridine bases through a continuous two-step process in a series-connected two-stage fixed-fed reactor. Firstly, dehydration of glycerol to acrolein was achieved in high selectivity over a catalyst FeP-P in the first reactor. The dehydration products were directly introduced into the second reactor charged with a bimetallic catalyst Cu4.6Pr0.3/HZSM-5, contacting ammonia over the catalyst to afford pyridine bases in high yield. Under optimized reaction conditions, the conversion of glycerol was 100%, and the total yield of pyridine base reached up to 60.2%. The catalyst characterization results revealed that the doping of copper and praseodymium did not destroy the frame work of HZSM-5, but increased the Lewis acidity of the catalyst which enhanced the activity and selectivity of the catalyst in the conversion of acrolein to pyridine bases. The doping of minute amount of praseodymium led to the high dispersion of the CuO nanoparticles, thus enhanced the dehydrogenation activity of CuO species, and finally improved the performance of the bimetallic catalyst. In addition, the interaction of copper and praseodymium in the bimetallic catalyst might have positive effect on the performance of the catalyst in the conversion of acrolein to pyridine bases.

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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

Extended knowledge of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Conjugate Additions of Amines to Maleimides via Cooperative Catalysis

A cooperative system comprising of a lithium Lewis acid and amine base significantly enhances the rate of the conjugate addition of a wide array of amines to maleimides. This operationally simple, scalable method provides mono-addition products in high yields and purity. This conjugation was successfully applied to the kinase inhibitor crizotinib in a chemoselective ligation to create novel fluorescent probe. (Figure presented.).

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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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Diels-Alder Cycloadditions of Diene-Substituted N-Ethoxycarbonyl-2-methyl-1,2-dihydropyridines with N-Phenylmaleimide

The ten possible substitution patterns for N-ethoxycarbonyl-2-methyl-1,2-dihydropyridines 5 in which one or two olefinic sites are alkyl substituted were synthesized and reacted with N-phenylmaleimide 2 to provide cycloadducts 6.N-ethoxycarbonyl-5,6-cyclohexyl-2-methyl-1,2-dihydropyridine 5l provided the novel spirocycle 6l.

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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