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Enantioselective acylation of 1,2- and 1,3-diols catalyzed by aminophosphinite derivatives of (1 S,2 R)-1-amino-2-indanol

A phosphinite derivative that can be easily prepared in two steps from commercially available aminoindanol was found to be an effective catalyst for enantioselective acylation of diols. For the asymmetric desymmetrization of meso-1,2-diols, the corresponding monoester was obtained in up to 95% ee from the reaction in the presence of 5 mol % 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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Catalytic Asymmetric Syntheses of Secondary Alcohols Using cis-1-Amino-2-indanols as Chiral Ligands

Both enantiomers of cis-1-amino-2-indanols (1a,b) have been used as chiral ligands in the catalytic asymmetric reduction of ketones with BH3*SMe2 affording secondary alcohols with enantiomeric excesses up to 95percent.Furthermore, some N,N-dialkyl derivatives of 1a,b catalyzed the enantioselective addition of diethylzinc to aldehydes.

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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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Hydrogen Bonding. Part 10. A Scale of Solute Hydrogen-bond Basicity using log K Values for Complexation in Tetrachloromethane

A scale of solute hydrogen-bond basicity has been set up using log K values for the complexation of a series of bases (i) against a number of reference acids in dilute solution in tetrachloromethane, equation (i). log Ki = LA log KBH + DA (i) Thirty-four such linear equations have been solved to yield 1, and 0, values that characterise the acids, and log KBH values that characterise the base; all the thirty-four equations intersect at a point where log K = -1.1 with K on the molar scale. This primary set of log Kz values involved 215 bases, and through a large number of secondary values we have been able to determine log KBH for some 500 bases, that include nearly all the functional groups encountered in organic chemistry. By making use of the ‘magic point,’ we have transformed log KBH into an entirely equivalent, but more convenient, scale through equation (ii). beta2H = (log KBH + 1.1)/4.636 (ii) Since we can take beta2H = 0 for all non-basic compounds such as alkanes and cycloalkanes, the new beta2H; hydrogen-bond solute basicity scale covers virtually all classes of base. We show that beta2H is not generally related to measures of full proton-transfer basicity such as aqueous pK or gaseous proton affinity (Epa) values, although family dependence is observed, and we stress that solute hydrogen-bond basicity must not be equated with full proton-transfer basicity. We also briefly investigate the solvent dependence of the beta2H values in terms of the Maria-Gal theta value, and we point out a number of exclusions to the ‘reasonably general’ beta2H scale

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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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Matrix metalloproteinase inhibitors: A structure-activity study

Modifications around the dipeptide-mimetic core of a hydroxamic acid based matrix metalloproteinase inhibitor were studied. These variations incorporated a variety of natural, unnatural, and synthetic amino acids inaddition to modifications of the P1′ and P3′ substituents. The results of this study indicate the following structural requirements: (2) Potent inhibitorsmust possess string zinc-binding functionalities. (3) The potential importance of the hydrophobic group at position R3 as illustratedby itsability to impart greater relative potency against stromelysin when larger hydrophobic groups are used. (4) Requirements surrounding the nature of the amino acid appear to be more restrictive for stromelysin than for neutrophil collagenase, 72 kDa gelatinase, and 92 kDa gelatinase. These requirements may involve planar fused-ring aryl systems and possibly hydrogen-bonding capabilities.

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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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HIGH PRESSURE NQR STUDIES OF HYDROGEN BONDS FOR COMPLEXES OF PENTACHLOROPHENOL WITH NITROGEN BASES

The NQR spectrum of 35Cl nuclei for complexes of pentachlorophenol with nitrogen bases has been studied as a function of pressure and temperature.It is shown that the value of the pressure coefficient of the NQR frequency is related to the degree of proton transfer.A distinct anomaly of the pressure coefficient of the NQR frequency in the vicinity of 50percent proton transfer hydrogen bonds has been observed.The phenomena have been interpreted on the basis of the Matsushita and Matsubara model and by assuming the pressure dependence of proton transfer equilibrium.The influence of the crystal effect and torsional vibrations on the temperature-pressure characteristics of the NQR spectrum is discussed.

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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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Multinuclear NMR spectra of [Pt(L)Cl3]- (L = pyridine derivatives) complexes and crystal structure of trans-Pt(2,6-di(hydroxymethyl)pyridine)2Cl2.2H 2O

Complexes of the type [Pt(L)Cl3]- (L = pyridine derivative) were synthesized and studied by 13C and 195Pt NMR spectroscopies. The 195Pt signals were observed between -1720 and -1897 ppm. No correlation between the delta(Pt) and the pKa of the protonated pyridine derivatives was found. The chemical shifts vary with the substituents on the pyridine ligand. Compounds with substituents in ortho positions were observed at lower fields, except for complexes containing hydroxy or amine groups. The latter compounds were observed at higher fields, close to the signals of the Pt-unsubstituted pyridine compound. These results were explained in terms of the solvent effect. The chemical shifts delta(C) and the coupling constants J(13C-195Pt) were measured and the results interpreted with a view of obtaining information on the nature of the Pt – N bond. The possibility of pi-bonding between platinum and the pyridine ligand is examined. The conformation of the pyridine ring in relation to the platinum plane and the energies of the rotation barriers around the Pt – N bond in these types of platinum(II) complexes are briefly discussed. The crystal structure of trans-Pt(2,6-(HOCH2)2py)2Cl2-2H 2-O was determined by X-ray diffraction. The compound is monoclinic, C2/m, a = 7.022(6), b = 15.646(13), c = 8.344(10) A, ss= 93.35(8), Z = 2, R = 0.037. The platinum atom is located at the junction of the twofold axis and the mirror plane, the N atoms and the para-C atom of the pyridine ring are situated on the twofold axis, and the chloride ligands are on the mirror plane. The compound crystallizes with molecules of water, which are H-bonded to the hydroxy groups. The Pt – Cl bond distance is 2.306(2) A, and that of the Pt – N bond is 2.041(6) A. The dihedral angle between the platinum and the pyridine planes is 79.8.

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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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One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, Application In Synthesis of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, such as the rate of change in the concentration of reactants or products with time.In a article, mentioned the application of 126456-43-7, Name is (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, molecular formula is C9H11NO

Design, synthesis and trypanocidal activity of lead compounds based on inhibitors of parasite glycolysis

The glycolytic pathway has been considered a potential drug target against the parasitic protozoan species of Trypanosoma and Leishmania. We report the design and the synthesis of inhibitors targeted against Trypanosoma brucei phosphofructokinase (PFK) and Leishmania mexicana pyruvate kinase (PyK). Stepwise library synthesis and inhibitor design from a rational starting point identified furanose sugar amino amides as a novel class of inhibitors for both enzymes with IC50 values of 23 muM and 26 muM against PFK and PyK, respectively. Trypanocidal activity also showed potency in the low micromolar range and confirms these inhibitors as promising candidates for the development towards the design of anti-trypanosomal drugs.

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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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Mutual solubility of water and pyridine derivatives

Mutual binary solubilities have been measured for derivatives of pyridine and piperidine. Data are given for 36 water-organic pairs at temperatures of 0-90 C. It was found that 9 binary systems were miscible in all proportions over the temperature range, 14 showed partial solubility over the entire temperature range, and 13 were partially soluble at higher temperatures, but had lower critical solution temperatures and were completely miscible with water at lower temperatures. The very large number of systems exhibiting a lower critical solution temperature indicates that this feature is characteristic for these compounds.

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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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LOW TEMPERATURE STRUCTURE AND PHYSICAL PROPERTIES OF N-METHYL,2,4-DIMETHYL PYRIDINIUM (TCNQ)2.

The low-temperature (approximately 173 K) structure of NMe2,4MePy(TCNQ)//2 was determined and compared with the room-temperature structure. Electrical, magnetic, dielectric, and spectroscopic properties of the salt are reported. Detailed discussion of the transport properties is presented in terms of a one-electron semiconductor model with low-temperature behavior controlled by electrically active impurities.

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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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Novel inhibitor of p38 MAP kinase as an anti-TNF-alpha drug: Discovery of N-[4-[2-ethyl-4-(3-methylphenyl)-1,3-thiazol-5-yl]-2-pyridyl]benzamide (TAK-715) as a potent and orally active anti-rheumatoid arthritis agent

The p38 mitogen-activated protein (MAP) kinase has been implicated in the proinflammatory cytokine signal pathway, and its inhibitors are potentially useful for the treatment of chronic inflammatory diseases such as rheumatoid arthritis (RA) and inflammatory bowel disease. To develop a new drug for RA, we synthesized a novel series of 4-phenyl-5-pyridyl-1,3-thiazoles and evaluated their inhibition of p38 MAP kinase, lipopolysaccharide (LPS)-stimulated release of tumor necrosis factor-alpha (TNF-alpha) from human monocytic THP-1 cells in vitro, and LPS-induced TNF-alpha production in vivo in mice. During the course of the study, we found that these compounds risk the inhibition of cytochrome P450 (CYP) isoforms by coordination of the 4-pyridyl nitrogen with heme iron. We therefore investigated the effects of substitution at the 2-position of the pyridyl ring on the inhibitory activity of p38 MAP kinase and CYPs in more detail. As a result, N-[4-[2-ethyl-4-(3-methylphenyl)-1,3-thiazol- 5-yl]-2-pyridyl]benzamide (8h, TAK-715) exhibited potent inhibitory activity in these assays (inhibition of p38alpha, IC50 = 7.1 nM; LPS-stimulated release of TNF-alpha from THP-1, IC50 = 48 nM; LPS-induced TNF-alpha production in mice, 87.6% inhibition at 10 mg/kg, po) and no inhibitory activity for major CYPs, including CYP3A4. This compound also showed good bioavailability in mice and rats and significant efficacy in a rat adjuvant-induced arthritis model. Compound 8h was selected as a clinical candidate and is now under clinical investigation for the treatment of RA.

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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