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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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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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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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(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

The Shocking Revelation of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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A synthesis of (1S,2R)-1-amino-2-indanol (1), a key component of an HIV protease inhibitor, was accomplished through (R)-2-hydroxy-1-indanone ((R)- 3), which was prepared by an intramolecular Friedel-Crafts acylation of (R)2- acetoxy-3-phenylpropanoic acid readily available from D-(R)-phenylalanine. Alternatively, (R)-3 was obtained by an enzymatic resolution of (±)-2- acetoxy-1-indanone. Ketone (R)-3 was convened into 1 through an oxime formation and diastereoselective hydrogenation.

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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 disclosure provides processes for the preparation of a compound of formula I: which is useful as an antiviral agent. The disclosure also provides compounds that are synthetic intermediates to compounds of formula I.

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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 dipole moments of eight pyridines, three quinolines and acridine, and of their hydrogen-bonded complexes with phenol have been determined in carbon tetrachloride solution at 20 deg C.The data points for the correlation of the dipole moments with the ability of the proton acceptors to associate with phenol and with their basicity, are separated into two groups.In one group the compounds possess a resultant of the group moments that reinforces, whereas in the other group the resultant opposes the molecular dipole moment.The vectorially calculated dipole moments of the hydrogen-bonded complexes were found to be smaller than the corresponding dipole moments obtained experimentally.

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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

Never Underestimate The Influence Of 2,4-Dimethylpyridine

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Diols exhibiting the structure (HO)CH2-(CH2) n-CH2(OH) with n = 1 up to n = 4, (HO)CH 2-CH(OH)-CH3 and cyclohexan-1,2-diols as well as cyclohexan-1,4-diol, which may establish different intramolecular interactions, are used as model substances to describe the external hydrogen bonding behaviour of multivalent hydrogen bond donors in the presence of hydrogen bond acceptor molecules. In this study, hydrogen bonds formed by the diols with tertiary aromatic amines have been investigated. In solution, different associate formation between the diols and the acceptor molecules as sketched in Fig. 1 may occur. Besides 1:1 associates formed by the interaction of one diol molecule with one amine molecule, 1:2 associates may be observed where each OH function interacts with one amine molecule. The equilibrium constants of the associates of those interactions have been studied by FTIR spectroscopy. The results allow a classification of the used diols in three different groups based on the position of the OH groups in the donor molecule. For diols with proton donating OH where no intramolecular hydrogen bond can be formed, the intermolecular hydrogen bonds for a 1:1 system may be described by thermodynamic parameters which are nearly twice the value of the corresponding equilibrium constants of monovalent alcohol systems due to the statistical weight of the OH groups. Secondly, when intramolecular hydrogen bond exists in the diols, the equilibrium constants in the interaction with the amine raise up by a factor of ca. 2-3 due to the cooperativity effect. Thirdly, if the OH groups are arranged in 1,2 positions, both OH groups may be described as independent of each other in their intermolecular interaction with the amine.

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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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With the aim of developing small molecular non-peptide beta-secretase (BACE) inhibitors, Leu*Ala hydroxyethylene (HE) was investigated as a scaffold to design and synthesize a series of compounds. Taking advantage of efficient combinatorial synthesis approaches and molecular modeling, extensive structure-activity relationship (SAR) studies were carried out on the N- and C-terminal residues of the Leu*Ala HE scaffold. Isobutyl amine was found to be an optimal C-cap, and suitable hydroxylalkylamines at the 3-position and nitro or methyl(methylsulfonyl)amine at the 5-position of isophthalamide as the N-terminus could form additional hydrogen bonds with BACE active sites and help improve potency. Many new potent non-peptide BACE inhibitors were identified in this study. Among them, compounds 37 and 44 exhibited excellent enzyme-inhibiting potency, comparable to that of OM99-2, and obvious inhibitory effects in cell-based assay with low molecular weights (<600). Because enzymes can increase reaction rates by enormous factors and tend to be very specific, they are the focus of active research. Each step is an elementary reaction. In my other articles, you can also check out more blogs about 126456-43-7 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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Overlapping peaks interfere in ion mobility spectrometry (IMS), but they are separated introducing mobility shift reagents (SR) in the buffer gas forming adducts with different collision cross-sections (size). IMS separations using SR depend on the ion mobility shifts which are governed by adduct’s size and interaction energies (stabilities). Mobility shifts of valinol and ethanolamine ions were measured by electrospray-ionization ion mobility-mass spectrometry (MS). Methyl-chloro propionate (M) was used as SR; 2-butanol (B) and nitrobenzene (N) were used for comparison. Density functional theory was used for calculations. B produced the smallest mobility shifts because of its small size. M and N have two strong interaction sites (oxygen atoms) and similar molecular mass, and they should produce similar shifts. For both ethanolamine and valinol ions, stabilities were larger for N adducts than those of M. With ethanolamine, M produced a 68% shift, large compared to that using N, 61%, because M has a third weak interaction site on the chlorine atom and, therefore, M has more interaction possibilities than N. This third site overrode the oxygen atoms’ interaction energy that favored the adduction of ethanolamine with N over that with M. On the contrary, with valinol mobility shifts were larger with N than with M (21 vs 18%) because interaction energy favored even more adduction of valinol with N than with M; that is, the interaction energy difference between adducts of valinol with M and N was larger than that between those adducts with ethanolamine, and the third M interaction could not override this larger difference. Mobility shifts were explained based on the number of SR’s interaction sites, size of ions and SR, and SR-ion interaction energies. This is the first time that the number of interaction sites is used to explain mobility shifts in SR-assisted IMS.

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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