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Aryne [3 + 2] cycloaddition with N-sulfonylpyridinium imides and in situ generated N-sulfonylisoquinolinium imides: A potential route to pyrido[1,2-b]indazoles and indazolo[3,2-a]isoquinolines

The aryne [3 + 2] cycloaddition process with pyridinium imides breaks the aromaticity of the pyridine ring. By equipping the imide nitrogen with a sulfonyl group, the intermediate readily eliminates a sulfinate anion to restore the aromaticity, leading to the formation of pyrido[1,2-b]indazoles. The scope and limitation of this reaction are discussed. As an extension of this chemistry, N-tosylisoquinolinium imides, generated in situ from N?-(2-alkynylbenzylidene)-tosylhydrazides via an AgOTf-catalyzed 6-endo-dig electrophilic cyclization, readily undergo aryne [3 + 2] cycloaddition to afford indazolo[3,2-a]-isoquinolines in the same pot, offering a highly efficient route to these potential anticancer agents.

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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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Finite molecular assemblies in the organic solid state: toward engineering properties of solids

Assemblies of organic molecules that form finite structures represent targets for crystal engineers that can exhibit properties largely independent of crystal packing. Such finite molecular assemblies can display function, such as host-guest behavior and chemical reactivity. Here, we provide a review of finite molecular assemblies characterized in the organic solid state. The assemblies are classified as being either purely synthetic or functional. Examples from both the areas are presented and 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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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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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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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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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 Absolute Best Science Experiment for (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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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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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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Volumes of mixing 2,4-dimethylpyridine with n-alkanes

In continuation of our work on excess thermodynamic properties of non-electrolyte solutions containing pyridine bases with n-alkanes, we have determined excess molar volumes VE for 2,4-ditnethylpyridine + C6 to C10 n-alkanes at 25C. For the investigated systems no VE values were available in the literature for compari1 son with our data. The experimental VE was used to test the Prigogine-Flory-Patterson theory (PFP), Extended Real Associated Solutions model (ERAS) and the Treszczanowicz-Benson method (TB).

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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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ALPHA-7 NICOTINIC RECEPTOR MODULATORS FOR THE TREATMENT OF PAIN, A PSYCHOTIC DISORDER, COGNITIVE IMPAIRMENT OR ALZHEIMER’S DISEASE

Compounds are disclosed which modulate the alpha7 nicotinic acetyl choline receptor (nAChR), having the formula (I) wherein the variables are as specified in the description and claims

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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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Design and synthesis of a series of (2R)-N4-hydroxy-2-(3-hydroxybenzyl)-N1- [(1S,2R)-2-hydroxy-2,3-dihydro-1H-inden-1-yl]butanediamide derivatives as potent, selective, and orally bioavailable aggrecanase inhibitors

A pharmacophore model of the P1? site, specific for aggrecanase, was defined using the specificity studies of the matrix metalloproteinases and the similar biological activity of aggrecanase and MMP-8. Incorporation of the side chain of a tyrosine residue into compound I as the P1? group provided modest selectivity for aggrecanase over MMP-1, -2, and -9. A cis-(1S)(2R)-amino-2-indanol scaffold was incorporated as a tyrosine mimic (P2?) to conformationally constrain 2. Further optimization resulted in compound 11, a potent, selective, and orally bioavailable inhibitor of aggrecanase.

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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