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(Equation presented) A practical synthesis of sultams was developed via intramolecular sulfonamide dianion alkylation. This method has been applied toward the synthesis of chiral sultams, which are synthetically valuable as chiral auxiliaries.

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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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An improved process using chiral hydrogenation is described for the synthesis in high yields of a 4-protected-(S)-piperazine-2-tert-butylcarboxamide, an intermediate for an HIV protease inhibitor.

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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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Sphingomonas paucimobilis strain EPA505 is capable of utilizing many components of coal tar creosote as sole sources of carbon and energy for bacterial growth, including fluoranthene and other polycyclic aromatic hydrocarbons (PAH). During several bioremodiation studies, however, we observed that the fluoranthene degradative activity of strain EPA505 was inhibited by the presence of undefined creosote constituents. In practice, integration of a pretreatment step prior to inoculation with strain EPA505 was necessary to facilitate the biodegradation of high molecular weight (HMW) PAHs. Experiments were thus initiated to determine which compound classes in creosote inhibited fluoranthene metabolism by strain EPA505. Creosote was fractionated by solvent extraction at various pH, and three chemical classes were examined: acid (phenolics), base (N-hetarocyclics), and neutral (PAH). The mineralization rate of 14C-labeled fluoranthene and cell viability were examined in the presence of these creosote fractions at a range of concentrations. These studies confirm that strain EPA505 has differing susceptibility to the effects of the three classes of creosote constituents. The observed order of toxicity/inhibition was basic fraction > acidic fraction > neutral fraction. These studies provide engineering guidelines and define contamination ranges under which strain EPA505 can be used most effectively as a catalyst in bioremediation (Figure 4). Sphingomonas paucimobilis strain EPA505 is capable of utilizing many components of coal tar creosote as sole sources of carbon and energy for bacterial growth, including fluoranthene and other polycyclic aromatic hydrocarbons (PAH). During several bioremediation studies, however, we observed that the fluoranthene degradative activity of strain EPA505 was inhibited by the presence of undefined creosote constituents. In practice, integration of a pre-treatment step prior to inoculation with strain EPA505 was necessary to facilitate the biodegradation of high molecular weight (HMW) PAHs. Experiments were thus initiated to determine which compound classes in creosote inhibited fluoranthene metabolism by strain EPA505. Creosote was fractionated by solvent extraction at various pH, and three chemical classes were examined: acid (phenolics), base (N-heterocyclics), and neutral (PAH). The mineralization rate of 14C-labeled fluoranthene and cell viability were examined in the presence of these creosote fractions at a range of concentrations. These studies confirm that strain EPA505 has differing susceptibility to the effects of the three classes of creosote constituents. The observed order of toxicity/inhibition was basic fraction > acidic fraction > neutral fraction. These studies provide engineering guidelines and define contamination ranges under which strain EPA505 can be used most effectively as a catalyst in bioremediation.

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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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Nickel hydride complexes, defined herein as any molecules bearing a nickel hydrogen bond, are crucial intermediates in numerous nickel-catalyzed reactions. Some of them are also synthetic models of nickel-containing enzymes such as [NiFe]-hydrogenase. The overall objective of this review is to provide a comprehensive overview of this specific type of hydride complexes, which has been studied extensively in recent years. This review begins with the significance and a very brief history of nickel hydride complexes, followed by various methods and spectroscopic or crystallographic tools used to synthesize and characterize these complexes. Also discussed are stoichiometric reactions involving nickel hydride complexes and how some of these reactions are developed into catalytic processes.

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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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Self-assembly of a stereodynamic phosphine ligand, Pd(II), and a chiral amine, amino alcohol, or amino acid generates characteristic UV and CD signals that can be used for quantitative stereochemical analysis of the bound substrate. A robust mix-and-measure chiroptical sensing protocol has been developed and used to determine the absolute configuration, ee, and yield of an amine produced by Ir-catalyzed asymmetric hydrogenation of an iminium salt. The analysis requires only 1 mg of the crude reaction mixture and minimizes cost, labor, time, and waste.

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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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Ultrasound-assisted extraction (UAE) of polysaccharide from Maryland tobacco leaves was studied by response surface methodology. Furthermore, the crude polysaccharide was purified and two components (Fr-I and Fr-II) were obtained. FT-IR spectral analysis of the purified polysaccharide revealed prominent characteristic groups. The monosaccharide composition analysis by gas chromatography-mass spectrometry (GC/MS) indicated the main composition between Fr-I and Fr-II was different. Furthermore, thermo gravimetric analysis (TGA) indicated the degradation temperature (Td) of the Fr-I (241C) was higher than those of Fr-II (216o C). Detected by the pyrolysis gas chromatography-mass spectrometry (py-GC/MS), it was found that the main kinds of pyrolysis products from both Fr-I and Fr-II were similar. Finally, On the basis of hydroxyl and DPPH radical scavenging assay, Fr-II has stronger antioxidant activities than Fr-I. The thermal behavior and antioxidant activity might be attributed to the configuration of the chemical 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

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Investigations into the mechanistic aspects of the stereospecific interaction of the four optical isomers of aminoindanol on a silica based crown ether column were performed. The nature and concentration of the mobile phase’s counteranion affected the hydrophobic interaction but had little effect on the inclusion interaction. Minimal changes in the separation factor of the enantiomers were observed in the pH range of 1-5.2, but a minimum in the capacity factor was observed at pH 3.75. Van’t Hoff plots indicated a high entropy and a positive enthalpy at pH 5.2, while a lower entropy and a negative enthalpy were observed at and below pH 3.75. Hill plots indicated that there were more active binding sites at pH 3.0 as compared to pH 1.0 and that the binding ratio of aminoindanol to active sites was also greater. Apparently at higher pH values, as the silica becomes deprotonated, there is an additional electrostatic interaction between the protonated aminoindanol and the deprotonated silica 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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Enantiomerically pure phosphinamides containing a pendant hydroxyl group catalyse the Al(III)-promoted ring opening of the meso epoxide in cyclohexene oxide with thiophenol in up to 80% enantiomeric excess.

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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 kinetics of the displacement of coordinated nitrogen donor bases (L)by chloride from complexes of the type [Pt(NSN)(L)](2+) [NSN=bis(2-pyri dylmethyl)sulphide; L=a series of pyridines, isoquinoline and NH3] as well as chloride substitution from the substrate [Pt(NSN)Cl](+) by Br(-) and I(-) have been studied in methanol at 25°C and constant ionic strength and compared with those of the corresponding platinum(II) complexes containing the 2,6-bis(methylsulphanyl)pyridine tridentate ligand. The two-term rate law usually found in substitutions at square-planar platinum(II) complexes is obeyed. Both the first and second-order rate constants for the displacement of L decrease as the basicity of the leavinggroup increases. pi interactions between coordinated pyridines and th e metal centre are suggested by comparison of their lability with that of ammonia as well as with that of para-substituted pyridines with enhanced pi system. Steric hindrance on the leaving base also significantly decreases the reactivity.

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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 Host compound 2,2? bis(1-hydroxy-4,5-dihydro-2,3:6,7-dibenzocycloheptatrien-1-yl)-biphenyl, H1, has been employed to discriminate between all the pairs of lutidine isomers. The preference for guest enclathration follows the sequence 3,4-LUT>2,4-LUT?3,5-LUT>2,5-LUT>2,3-LUT>2,6-LUT. This has been confirmed by guest-release endotherms measured by DSC. Four other diol host compounds, H2?H5, were tested on pairs of lutidine isomers which were poorly separated by H1.

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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