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Microwave and solvothermal activation processes have been explored as tools for the preparation of various nickel and ruthenium complexes. Different reaction conditions are tested using ethanol or water as solvents. Three nickel derivatives, [Ni(9-atc)2(OH2)2(py)2]·2EtOH (1), [Ni2(9-atc)4(OH2)(py)4]·2H2O (2·2H2O), and [Ni2(9-atc)4(py)2] (3), and two diruthenium compounds, {[Ru2Cl(9-atc)4]·2H2O}n (4) and [Ru2(9-atc)4(EtOH)2]·2EtOH (5), are obtained. The crystal structure determination of complexes 1-3 and 5 is also described. Compound 1 displays a 1D extended supramolecular structure with hydrogen bonds involving crystallization solvent molecules. Compound 2 is dimetallic, and both nickel centers show an octahedral coordination environment, whereas complexes 3 and 5 display a typical carboxylate-bridged paddlewheel-type structure with two metal atoms connected by four bridging carboxylate ligands. All compounds show weak antiferromagnetic interactions except 3, where a strong intra-dimer antiferromagnetic coupling is observed. Compound 4 also shows a strong zero field splitting.

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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 efficient copper-catalyzed selective cross coupling of imidazo[1,2-a]pyridines with methyl hetarenes has been reported. This transformation opened a new route to synthesize the C-3 carbonyl imidazo[1,2-a]pyridine derivative, which is a common structural motif in natural products and pharmaceuticals. 18O-labeling experiments indicated that the oxygen source of products originated from O2.

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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 invention relates to a process for preparing alkyl chlorides by reacting alcohols with gaseous hydrogen chloride in the presence of a catalyst, wherein the catalyst comprises at least one compound of the structure: wherein R1 is a linear alkyl group having from 1 to 20 carbon atoms, R2, R3, and R4 is selected from a hydrogen, an alkyl, an alkenyl, an aralkyl or an alkylaryl group from 1 to 20 carbon atoms, wherein the substituents of R2, R3, and R4 are all identical, are all different or two of the substituents of R2, R3, and R4 type are identical.

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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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Various chiral bidentate oxazoline-alcohol ligands were obtained in a straightforward one-step synthesis via a cyclic imidate ester rearrangement. These chiral ligands were tested and compared in asymmetric diethylzinc additions to aldehydes resulting in selectivities of up to 87% ee. An interesting chirality switch was observed when a CPh2-tether instead of a CH2 was present, offering the opportunity for dual stereocontrol.

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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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Optically pure inden-1-ol has been obtained efficiently in both enantiomeric forms via kinetic deacylation of racemic 1-acetoxyindene using lipase PS.

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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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Highly stereoselective asymmetric 6pi-azaelectrocyclization was achieved with generality, based on the reaction between the (E)-3-carbonyl-2,4,6-trienal compounds and the (-)-7-alkyl-cis-1-amino-2-indanol derivatives as the effective novel chiral amines. Furthermore, the chiral auxiliaries of the cyclized products obtained were efficiently removed by the novel manganese dioxide oxidation under remarkably mild conditions, and the method was successfully applied to the formal synthesis of optically active 20-epiuleine. 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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Gold(I) complexes of overall formula LAuCl (L = various methylpyridines) are non-conducting in acetone. X-ray structure analyses show that the solid state structure of the corresponding complex 1 (L = 2-picoline) is molecular; the 3-picoline derivative 2 is however ionic (L2Au)+(AuCl2)-. 3-Picoline forms a molecular complex LAuC6F5 (3) and also the ionic (L2Au)+(SbF6)- (4). Complexes 1, 2 and 4 display short Au…Au contacts, leading to chains of gold atoms; additionally, complexes 3 and 4 show weak Au…F contacts. The (3-picoline)-gold(III) complex trans-(L2AuCl2)+(SbF6)- (5) was obtained as a by-product; it too contains short Au…F contacts.

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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 hydrogen-bonding interaction between a series of methyl-substituted pyridines as proton acceptors and thioacetamide as a proton donor in CCl4 has been investigated using near-infrared absorption spectroscopy. The stability of the 1:1 hydrogen-bonded complex increases with the number of methyl groups and depends on the position of methyl groups. The steric hindrance of ortho-methyl groups particularly reduces the stability of complex. The relative stability agrees with the ease of miscibility of pyridines with water for methyl and dimethyl homologs. The calculated proton affinities and the DFT association energies using 6-31+G(d,p) and 6-311++G(2d,2p) basis sets reveal the steric hindrance of ortho-methyl groups.

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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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In conclusion, we affirm that quantitative kinetic descriptions of catalytic behavior continue to serve as an indispensable tool to navigate research efforts intended to model. If you are interested in 108-47-4, you can contact me at any time and look forward to more communication. Formula: C7H9N

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A 13C DNMR study of meso-1,1-bi(2-methylpiperidine) (7), meso-1,1′-bi(cis-2,4-dimethylpiperidine) (8), and meso-1,1′-bi(cis-4-tert-butyl-2-methylpiperidine) (9) with the aid of molecular mechanics calculation of the corresponding hydrocarbons 1,1′-bi(2-methylcyclohexane) (14), 1,1′-bi(cis-2,4-dimethylcyclohexane) (15), and 1,1′-bi(cis-4-tert-butyl-2-methylcyclohexane) (16) is reported.The most stable conformations of the bipiperidines are the enantiomeric conformations in which the lone pairs of the nitrogen atoms are approximately gauche to each other.In these conformations the N-N bond and all of the alkyl groups are equatorial to each of the chair-form piperidine rings.The energy barriers (DeltaG*) to the interconversion between these enantiomeric gauche conformations in 7, 8, and 9 are 12.5(-25 deg C), 17.7(+72 deg C), and 19.0 kcal mol-1 (+97 deg C), respectively.While the barrier for 7 is assigned to the passing inversion of the nitrogen atoms, the barriers for 8 and 9 are assigned to the single-passing rotation about the N-N bond.In the case of 7, the next stable conformations, in which one of the methyl groups is axial, were observed at the lower temperatures.The free energy difference between the next stable and the most stable conformations is 0.55 kcal mol-1 at -117 deg C, and the energy barrier between these conformations is 9.2 kcal mol-1 at -82 deg C, which is assigned to the ring inversion.

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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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Complexes of boron trifluoride with a series of substituted pyridines have been studied using a direct, low temperature (13)C and (19)F n.m.r. technique.At temperatures from 0 to -40 deg C, ligand exchange is slow enough to permit the observation of separate (13)C n.m.r. signals for bulk and co-ordinated pyridine molecules.The co-ordinated pyridine shift displacements are interpreted in terms of ligand polarization and a paramagnetic effect at the nitrogen atom.The BF3 (19)F n.m.r. chemical shifts were correlated with calorimetric data in several cases, and in general provide a measure of the strenght of the interaction but not of ligand basicity.Comparative complexing abilities were evaluated by studying several pyridine mixtures.

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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