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A series of methylated and octylated pyridinium and quinolinium containing thiourea salts with a chiral 2-indanol substituent are reported. These organocatalysts are positively charged analogues of privileged bis(3,5-trifluoromethyl)phenyl substituted thioureas, and are found to be much more active catalysts despite the absence of an additional hydrogen bond donor or acceptor site (i.e., the presence of a heteroatom-hydrogen or heteroatom). Friedel-Crafts reactions of trans-beta-nitorostyrenes with indoles are examined, and good yields and enantioselectivities are obtained. Mechanistic studies indicate that this is a second-order transformation under the employed conditions, and is consistent with the dimer of the thiourea being the active catalyst. Charged organocatalysts, consequently, represent an attractive design strategy for catalyst development.

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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 scope and mechanism of the isomerization of arylamines to methyl-substituted aromatic heterocycles have been studied.Aniline, toluidines, naphthylamines and m-phenylenediamine all reacted to the corresponding ortho-methyl-substituted aza-aromatiics when exposed to high NH3 pressure and elevated temperature in the presence of acid catalysts.Zeolites with a three-dimensional pore structure, especially H-ZSM-5, showed the best performance.Optimum reaction conditions are around 600 K and 10 MPa.Two mechanisms which had been proposed earlier for this apparent N-ortho C exchange reaction proved untenable.Neither incorporation of the N atom into the aromatic ring nor a mechanism based on an intramolecular Ritter reaction could explain the required high NH3 pressure or the product distribution.Two new mechanisms are proposed which can explain all observations.In both mechanisms, reaction starts with addition of NH3 to the arylamine, followed by ring opening.In one mechanism an alkyno-imine intermediate is formed; in the other mechanism an enamino-imine intermediate is formed through a reverse aldol reaction.In both cases ring closure and NH3 elimination lead to the required aromatic heterocycles.The high NH3 pressure is explained by the need to add NH3 to the aromatic ring, and the high temperature by the need to desorb NH3 from the acid sites.

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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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Lipase-mediated kinetic resolution of cis-1,2-indandiol 5 in the presence of lipase PS was examined. Enantiomerically enriched (1S,2R)-2-acetoxy-1-indanol 6a was obtained when cis-1,2-indandiol 5 was treated with one equivalent of vinyl acetate. Treatment of 5 with two equivalents of vinyl acetate furnished a mixture of (1R,2S)-2-acetoxy-1-indanol 6a and (1R,2S)-1-acetoxy-2-indanol 6b. A route to both enantiomers of 1 was also developed by using the enantiomerically enriched mono-acetate thus obtained.

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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 C,N double bond of pyridine, quinoline and isoquinoline as heterodipolarophile react with diarylnitrilimines 2, generated in situ by dehydrohalogenation of N-phenylbenzhydrazonoyl chlorides 1, in a cycloaddition with complete regioselectivity.A facile route to hitherto unreported 1,3-diaryl-1,8a-dihydro<1,2,4>triazolo<4,3-a>pyridines 3, 1,3-diaryl-3,3a-dihydro<1,2,4>triazolo<4,3-a>quinolines 4, and 1,3-diaryl-1,10b-dihydro<1,2,4>triazolo<3,4-a>isoquinolines 5 has been developed.In a similar way, cycloadditions are carried out with C-ethoxycarbonyl- and C-acetyl-N-phenylnitrilimines.The ring cleavage of 3 in acidic medium yields the corresponding <(arylhydrazono)methyl>pyridinium chlorides 7.The conversion of the open-chain products back to 3 has been carried out in pyridine containing triethylamine.Anodic oxidation of 3 – 5 in aprotic medium affords the <1,2,4>triazolohetarenium perchlorates 9 – 11.The yields in such reactions are either similar or better than with chemical oxidants.The thermally initiated cycloreversion of 3 and 5 is discussed, judging from the facts that the thermolysis afford 2:1 cycloadducts.Key Words: Nitrilimines / <1,2,4>Triazolopyridines / 1,3-Dipolar cycloadditions

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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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Reactions catalyzed within inorganic and organic materials and at electrochemical interfaces commonly occur at high coverage and in condensed media,name: 2,4-Dimethylpyridine, Name is 2,4-Dimethylpyridine, belongs to chiral-nitrogen-ligands compound, is a common compound. name: 2,4-Dimethylpyridine, In an article, authors is Wang, Tielin, once mentioned the new application about name: 2,4-Dimethylpyridine.

Aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and piperazine (PZ) appear to be commercially attractive solvents for post-combustion CO2 capture by absorption/stripping. An experimental study on the oxidative degradation of aqueous PZ solutions and AMP/PZ blends was carried out. The oxidative degradation experiments were performed in a 200mL glass batch reactor with an oxygen partial pressure of 250kPa, and at the temperatures of 80-120C. The amine loss was determined by cation ion chromatography (IC) while the degradation compounds were identified and quantified by gas chromatography-mass spectrometry (GC-MS), cation IC and anion IC. Possible chemical pathways of PZ oxidative degradation are proposed to account for the observed degradation products. As compared to oxidative degradation of single AMP and PZ solvents, no new product was observed in partially degraded AMP/PZ blends. However, PZ degraded faster in the blends than it degraded individually at identical degradation conditions.

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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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This work demonstrated the potential of using a secondary drift gas of differing polarizability from the primary drift gas for confirmation of a positive response for drugs or explosives by ion mobility spectrometry (IMS). The gas phase mobilities of response ions for selected drugs and explosives were measured in four drift gases. The drift gases chosen for this study were air, nitrogen, carbon dioxide and nitrous oxide providing a range of polarizability and molecular weights. Four other drift gases (helium, neon, argon and sulfur hexafluoride) were also investigated but design limitations of the commercial instrument prevented their use for this application. When ion mobility was plotted against drift gas polarizability, the resulting slopes were often unique for individual ions, indicating that selectivity factors between any two analytes varied with the choice of drift gas. In some cases, drugs like THC and heroin, which are unresolved in air or nitrogen, were well resolved in carbon dioxide or nitrous oxide.

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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 present invention provides a metallocenyl compound of formula (I). Ra, Rb, Rc, Rd, Re, Rf, M, m, n, j, k, Y and Z and * are as described in the specification. The invention also provides a process for the preparation of the complexes, a process for increasing the optical purity of a compound of formula (II) and a process for the asymmetric transfer hydrogenation (ATH) of a metallocenyl compound of formula (V) to a metallocenyl compound of formula (IV).

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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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Implementation of derivatized carbohydrates as C2-symmetric HIV-1 protease inhibitors has previously been reported. With the objective of improving the anti-HIV activity of such compounds, we synthesized a series of fluoro substituted P1/P1? analogues. These compounds were evaluated for antiviral activity toward both wild type and mutant virus. The potency of the analogues in blocking HIV-1 protease was moderate, with Ki values ranging from 1 to 7 nM. Nonetheless, compared to the parent nonfluorous inhibitors, a majority of the compounds exhibited improved antiviral activity, for example the 3-fluorobenzyl derivative 9b, which had a Ki value of 7.13 nM and displayed one of the most powerful antiviral activities in the cellular assay of the series. Our results strongly suggest that fluoro substitution can substantially improve antiviral activity. The X-ray crystal structures of two of the fluoro substituted inhibitors (9a and 9f) cocrystallized with HIV-1 protease are 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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Lignocellulosic biomass is considered an abundant and renewable source to produce bio-oils with an objective of its value addition for fuels and chemicals. Upgrading strategies have immensely evolved as a result of ever progressing research in this field. Development of complete analytical protocol for bio-oil characterization at different stages of its production, storage, upgrading and during its use is essential for the purpose of its quality assurance and understanding. This report is aimed at developing a sample preparation procedure for bio-oils involving an extensive liquid-liquid extraction approach. Bio-oil obtained after slow pyrolysis of Jatropha Curcas seed cake was phase separated and subjected to solvent extraction. Various solvents were screened for their extraction capabilities towards available organic compounds of all functional group in the bio-oil. Ethyl acetate, dichloromethane, carbon tetrachloride, diethyl ether, benzene, cyclohexane and hexane were employed for extraction of aqueous phase under similar conditions. Recoveries of compounds containing varying functional groups indicated ethyl acetate and dichloromethane as optimum among all other solvents. During the extraction, partitioning of compounds between bio-oil phase and solvent occurred largely on the basis of polarity. Acidic and basic organic compounds present in the aqueous phase were determined after adjusting the pH of samples followed by dichloromethane extraction. A comprehensive detail of the extracted chemicals and their classification has been provided. The identification was carried out qualitatively with GC-MS and derivatization of polar chemicals was also carried out before analysis. These experiments compare the efficacy of various organic solvents for extracting diverse bio-oil pyrolytic products. The findings are important in ascertaining usefulness of organic solvents towards enrichment of available bio-oil chemical groups. The information may be either utilized for characterization purposes or their monitoring during upgrading process.

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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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As an important bridge between the micro and macro material world, chemistry is one of the main methods and means for humans to understand and transform the material world. Quality Control of 3,4-Di(1H-indol-3-yl)-1H-pyrrole-2,5-dione, Name is 3,4-Di(1H-indol-3-yl)-1H-pyrrole-2,5-dione, belongs to chiral-nitrogen-ligands compound, is a common compound. Quality Control of 3,4-Di(1H-indol-3-yl)-1H-pyrrole-2,5-dioneCatalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. In an article, authors is , once mentioned the new application about Quality Control of 3,4-Di(1H-indol-3-yl)-1H-pyrrole-2,5-dione.

The present invention relates to novel melanocortin receptor modulators corresponding to the general formula (I) to compositions containing them, to the process for preparing them and to their use in pharmaceutical or cosmetic compositions.

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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