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The depolarized Rayleigh relaxation times and spin-lattice relaxation times of carbon-13 NMR for 2,4-dimethylpyridine (DP)-water and pyridine (PY)-water systems have been studied as a function of concentration and temperature.The conentration dependences of the mean-square-concentration fluctuation for these systems were also measured at various temperatures.The concentration fluctuation indicates that the solute molecules associate with each other at low concentration.The effect of the pair correlation on molecular orientational motion was derived from these relaxation times.The results show that solute molecules not only gather together but also align their orientation at low concentration.Since no pair correlation was observed for the neat liquid, it can be concluded that water molecules play an essentially important role for the aggregation of solutes.

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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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Starting from (eta5-acetylcyclopentadienyl)(eta4-tetraphenylcyclobutadiene)cobalt(I), highly enantioselective (99 % ee) (S)-CBS catalysed ketone reduction followed by stereospecific alcohol-azide exchange, azide reduction and dimethyllation gave (R)-(eta5-alpha-N,N-dimethylaminoethylcyclopentadienyl)(eta4-tetraphenylcyclobutadiene) cobalt(I) (Arthurs? amine). This underwent highly diastereoselective cyclopalladation to give di-mu-acetate-bis-(R)-[(eta5-(Sp)-2-(alpha-N,N-dimethylaminoethyl)cyclopentadienyl, 1-C, N)(eta4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium, and highly diastereoselective lithiation to give (R)-(eta5-(Sp)-1-(alpha-N,N-dimethylaminoethyl)-2-(diphenylphosphino)cyclopentadienyl)(eta4-tetraphenylcyclobutadiene)cobalt(I) (PPCA) following the addition as electrophile of chlorodiphenylphosphine. This PN-ligand was converted into (R)-(eta5-(Sp)-1-(alpha-dicyclohexylphosphinoethyl)-2-(diphenylphosphino)cyclopentadienyl)(eta4-tetraphenylcyclobutadiene)cobalt(I), a PP-ligand (Rossiphos), by stereospecific amine-phosphine exchange using HPCy2. These air-stable P?N and P?P complexes are the first examples of a new class of bulky planar chiral ligands for application in asymmetric 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

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Organocatalysts 1, derived from L-proline and (1S,2R)-cis-l-aminoindan-2-ol or (R)-l-aminoin-dane, are evaluated as promoters in the direct asymmetric aldol reaction between ketones and aromatic aldehydes in the presence of water and under solvent-free reaction conditions. L-Prolinethioamides 1c and 1d exhibited higher enantioselectivity than the corresponding prolinamides 1a and 1b in the model aldol reaction between cyclohexanone and 4-nitro-benzaldehyde in the presence of 4-nitrobenzoic acid as cocatalyst. In particular, L-prolinethioamide 1d (5 mol%), derived from L-proline and (R)-1-amino-indane, is shown as the most efficient organocatalyst studied promoting the direct aldol reaction of cyclo-alkyl, alkyl, and a-functionalized ketones with aromatic aldehydes in the presence of water and under solvent-free reaction conditions employing only 2 equivalents of nucleophile. Generally, anft-aldol products are obtained in high yields and excellent diastereo- and enantioselectivities (up to > 98/2 until syn, up to 98% ee). Solvent-free conditions give slightly higher dr and ee than using water as solvent. In addition, organocatalyst Id can be easily recovered by extractive work-up and reused. Prolinethio-amide Id (5 mol%) in combination with 4-NO2C6H4CO2H (5 mol%) is also a very effective or-ganocatalytic system for the asymmetric solvent-free intramolecular Haj os-Parrish-Eder-Sauer-Wiechert reaction with comparable or higher levels of enantioselectivity (up to 88% ee) to other reported catalysts in organic solvents.

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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 variety of Lewis bases were combined with 9-BBN-NTf2 to establish the requirements for the generation of borenium cations. Five different types of behaviors were found, but the most interesting was the combination of Et3N, DABCO, 2,6-lutidine, or Ph3P=S, which formed borenium ions exclusively even in sub- or superstoichiometric quantities. The 9-BBN borenium ion complex of 2,6-lutidine rapidly catalyzes the hydrosilylation of a variety of ketones in the presence of Et3SiH. Preliminary mechanistic experiments suggest that the reduction involves borenium ion activation of Et3SiH and not the ketone.

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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 effects of the shape of a methyl group on reactivity, which cannot be accounted for by considering a methyl group as a spherical subtituent with the appropriate van der Waals radius, was considered in kinetics of alkylation of substituted pyridines and barriers to rotation and ground state conformations of an isopropyl group attached to a planar framework.The perturbation of a methyl group by an o-methyl group is accounted for by a unique conformational explanation which involves the polyhedral shape of the methyl group.

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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 interactions of three cationic distyryl dyes, namely 2,4-bis(4-dimethylaminostyryl)-1-methylpyridinium (1 a), its derivative with a quaternary aminoalkyl chain (1 b), and the symmetric 2,6-bis(4- dimethylaminostyryl)-1-methylpyridinium (2 a), with several quadruplex and duplex nucleic acids were studied with the aim to establish the influence of the geometry of the dyes on their DNA-binding and DNA-probing properties. The results from spectrofluorimetric titrations and thermal denaturation experiments provide evidence that asymmetric (2,4-disubstituted) dyes 1 a and 1 b bind to quadruplex DNA structures with a near-micromolar affinity and a fair selectivity with respect to double-stranded (ds) DNA [Ka(G4)/K a(ds)=2.5-8.4]. At the same time, the fluorescence of both dyes is selectively increased in the presence of quadruplex DNAs (more than 80-100-fold in the case of human telomeric quadruplex), even in the presence of an excess of competing double-stranded DNA. This optical selectivity allows these dyes to be used as quadruplex-DNA-selective probes in solution and stains in polyacrylamide gels. In contrast, the symmetric analogue 2 a displays a strong binding preference for double-stranded DNA [Ka(ds)/K a(G4)=40-100), presumably due to binding in the minor groove. In addition, 2 a is not able to discriminate between quadruplex and duplex DNA, as its fluorescence is increased equally well (20-50-fold) in the presence of both structures. This study emphasizes and rationalizes the strong impact of subtle structural variations on both DNA-recognition properties and fluorimetric response of organic dyes. Copyright

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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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Improved, convenient, and reliable routes for synthesis of 4-,5-,6-, and 7-azaindole, 7-methyl-4-azaindole, 7-methyl-6-azaindole, and the hithero unreported 7-amino-4-azaindole are described.The syntheses have been accomplished either by significant modifications to established procedures or by new methods with afford the compounds in improved 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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A polyfluoroalkylation of pyrrole and phenols with freon BrCF2CF2Br using sulfur dioxide-substituted pyridine activating system proceeds at the aromatic nucleus by a free-radical mechanism. The essential influence of the basicity of the medium is demonstrated and discussed.

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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 reaction of the monoalkyl complex trans-[Pt(DMSO)2Cl(CH3)] with a large variety of heterocyclic nitrogen bases L, in chloroform solution, leads to the formation of uncharged complexes of the type [Pt(DMSO)(L)Cl(CH3)], containing four different groups coordinated to the metal center. Only two out of the three different possible isomers were detected in solution. These two trans(C,N) and cis(C,N) species can be unambiguously identified through 1H NMR spectroscopy. For the trans(C,N) isomers, average values of 2JPtH=75±4 Hz and 3JPtH=36±4 Hz have been observed for the coordinated methyl and DMSO ligands, respectively. In the case of the cis(C,N) isomers, these values increase to 2JPtH=83±2 Hz, and decrease to 3JPtH=26±3 Hz due to the mutual exchange of ligands in trans position to CH3 and DMSO. In the case of bulky asymmetric ligands, such as quinoline, 2-quinolinecarboxaldehyde, 2-methylquinoline, 5-aminoquinoline, 2-phenylpyridine and 2-chloropyridine, slow rotation of the hindered group around the Pt-N bond makes the coordinated DMSO ligand prochiral. NMR experiments have shown that the first reaction product is the trans(C,N) isomer as a consequence of the very fast removal of one DMSO ligand by the nitrogen bases from the starting complex trans-[Pt(DMSO)2Cl(CH3)]. This trans kinetic product undergoes a geometrical conversion into the more stable cis(C,N) isomer through the intermediacy of fast exchanging aqua-species. The rate of isomerization and the relative stability of the two isomers depends essentially on the rate of aquation and on the steric congestion imposed by the new L ligand on the metal.

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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 new metric is introduced for representing the molecular signature of atmospherically relevant organic compounds, the collision cross section quantity that is related to the structure and geometry of molecules and is derived from ion mobility measurements. By combination with the mass-to-charge ratio (im g iz ), a two-dimensional’g?im g iz space is developed to facilitate the comprehensive investigation of the complex organic mixtures. A unique distribution pattern of chemical classes, characterized by functional groups including amine, alcohol, carbonyl, carboxylic acid, ester, and organic sulfate, is developed on the 2-D ‘g?im g iz space. Species of the same chemical class, despite variations in the molecular structures, tend to situate as a narrow band on the space and follow a trend line. Reactions involving changes in functionalization and fragmentation can be represented by the directionalities along or across these trend lines, thus allowing for the interpretation of atmospheric transformation mechanisms of organic species. The characteristics of trend lines for a variety of functionalities that are commonly present in the atmosphere can be predicted by the core model simulations, which provide a useful tool to identify the chemical class to which an unknown species belongs on the ‘g?im g iz space. Within the band produced by each chemical class on the space, molecular structural assignment can be achieved by utilizing collision-induced dissociation as well as by comparing the measured collision cross sections in the context of those obtained via molecular dynamics simulations.

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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