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Seven uranyl(VI) complexes, [UO2(acac)2(L)] [L = 4- methylpyridine (1), 4-ethylpyridine (2), 2,4-dimethylpyridine (3), (-)-nicotine (4), and imidazole (5)], [{UO2(acac)2}2 – (4,4′-bipyridine)] (6), and [(2,2′-bipyridine)2H] [UO2(acac)- (NO3)2] (7) have been synthesized and characterized crystallographically. The coordination geometry of U has a UNO6 pentagonal-bipyramidal coordination in 16, and a UO8 hexagonal-bipyramidal coordination in 7.

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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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Pyrophthalones VII.Synthesis and anti-inflammatory activity of 2-(4-pyridinyl)indane-1,3-diones diversely substituted on the benzene ring.Access routes to 2-(1,4-dihydro 4-pyridinylidene) indane-1,3-diones diversely substituted on the benzene ring are studied.The regiospecific attack of these beta diketoenamines by alkyl iodides leads to N-substituted compounds.These derivatives may be obtained by any of three possible methods: (1) condensation of 4-methyl pyridine with ethyl phthalates in the absence of catalyst; (2) oxidative condensation of N-alkyl-pyridinium bromides with indane-1,3-diones; (3) aminolysis of 2-(4-4H-pyranylidene) indane-1,3-diones.Pharmacomodulation by the introduction of oxygen or sulfur containing functions (ether, thioether, alcohol, ketone, acid, ester, amide) on the nitrogen of the basic molecule is not very fruitful; only the acetic derivative 19 manifests marked antiinflammatory activity unaccompanied by anti-coagulant action.The presence of chloro, nitro or methoxyl groups on 5 after N-substitution by ethyl or piperidinylethyl groups appears to be more favorable.The most active compound 57 decreases prostaglandin production and leukocyte migration without affecting either cyclooxygenase or 5-lipoxygenase.Its interference, direct or indirect, with phospholipasic A2 activity may be envisaged in particular.Keywords – 2-(4-pyridinyl)indane-1,3-diones / heterocyclic beta diketoenamines / partition coefficient / anti-inflammatory activity / mechanism of action

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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 chapter presents the synthesis of heterocycles with a stereogenic phosphorus or sulfur atom derived from aminoalcohols or aminonaphthols, which has been reported recently (usually after 2002). It also contains selected references to the earlier papers and is divided into three sections, describing methods of synthesis of the three particular classes of heterocyclic derivatives. The first two are devoted to heterocycles with a stereogenic phosphorus atom and discuss the protocols for the preparation of 1,3,2-oxazaphospholanes (1,3,2-oxazaphospholidines) with a tri- and tetracoordinated phosphorus atom, 1,3,2-oxazaphosphorinanes and larger rings containing a stereogenic phosphorus atom forming part of the nitrogen-phosphorus-oxygen (NPO) grouping. The third section concerning heterocycles with a stereogenic sulfur atom describes the synthesis of all kinds of 1,2,3-oxathiazolidine 2-oxides and tetrahydro-1,2,3-oxathiazine-2-oxides.

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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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Different L-prolinamides 21, prepared from L-proline and chiral beta-amino alcohols are active bifunctional catalysts for the direct nitro-Michael addition of ketones to beta-nitrostyrenes. In particular, catalyst 21e, prepared from L-proline and (1S,2R?)-cis-1-amino-2-indanol, exhibits the highest catalytic performance working in polar aprotic solvents such as NMP, especially in the presence of 20 mol-% of acid additives such as p-nitrobenzoic acid or under microwave heating. High syn diastereoselectivities (up to 94 % de) and good enantioselectivities (up to 80 % ee) are obtained at room temp. Moreover, catalyst 21e can be easily recovered and reused. ESI-MS studies are used to characterize the intermediates assumed for the catalytic cycle. The stereochemical control attending Michael addition reactions between ketones and nitrostyrenes catalyzed by prolinamide derivatives 21 has been investigated with computational density functional methods. Transition-state energies for the rate-limiting C-C bond-forming step are calculated. Analysis of these structures indicates that hydrogen bonding plays an important role in catalysis, and that the energy barrier for Re-face attack to form syn-(4S,5R) products is lower than that for Si-face attack leading to syn-(4R,5S) products. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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 library of chiral hemisalen ligands (30) was realized. The ligands were synthesized by the condensation of salicylaldehyde derivatives with amino-alcohols (amino-indanol or substituted amino-ethanol) and characterized. These ligands associated with ruthenium (II) precursors were tested on the asymmetric transfer hydrogenation (ATH) of aromatic ketones by sodium formate in water. The different substituent pattern on the ligand (electronic and hindrance effects on different positions) as well as the ruthenium precursor were investigated. The best compromise in terms of conversion and chiral induction led to the complex [RuCl2(mesitylene)]2 coordinated to (1S,2R)-1-((E)-(3-(dimethyl(phenyl)silyl)-2-hydroxy-5-methoxy benzylidene) amino)-2,3-dihydro-1H-inden-2-ol (L25). It reduces acetophenone in 95% yield and 91% ee in 18 h at 30C.

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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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Hydroxyl groups on an unsaturated imine, which may be readily obtained from the corresponding unsaturated aldehyde and the 1,2-ethanolamine derivative, were found to efficiently activate a [4+4] dimerization reaction to produce the eight-membered 1,5-diazacyclooctane. A novel OH-pi interaction between the two imines, in addition to the stabilization of the eight-membered diacetals, was proposed based on density functional theory calculations. Georg Thieme Verlag Stuttgart New York.

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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 an effort to identify a new class of druglike HIV-1 protease inhibitors, four different stereopure beta-hydroxy gamma-lactam-containing inhibitors have been synthesized, biologically evaluated, and cocrystallized. The impact of the tether length of the central spacer (two or three carbons) was also investigated. A compound with a shorter tether and (3R,4S) absolute configuration exhibited high activity with a Ki of 2.1 nM and an EC50 of 0.64 muM. Further optimization by decoration of the P1? side chain furnished an even more potent HIV-1 protease inhibitor (Ki = 0.8 nM, EC50 = 0.04 muM). According to X-ray analysis, the new class of inhibitors did not fully succeed in forming two symmetric hydrogen bonds to the catalytic aspartates. The crystal structures of the complexes further explain the difference in potency between the shorter inhibitors (two-carbon spacer) and the longer inhibitors (three-carbon spacer).

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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 this paper we present experimental results for the optical dichroism of ultra-thin layers of an epitropic liquid crystal, 2,6-lutidine, on a carbonized quartz substrate. The carbon layer consists of carbon chains with an orientation perpendicular to the substrate surface. It significantly enhances the orientational order of the lutidine layers adjacent to the surface. A two-fold increase of the orientational order parameter S for 2,6-lutidine (from 0.22 to 0.45) has been measured due to the influence of the carbon layer. The inclusion of nitrogen atoms (nN = 7%) into the carbon film leads to a further increase of S from 0.45 to 0.65.

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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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Nineteen substituted enamides 4 are easily prepared (yields 30-71percent) in chloroform by condensation of various acyl chlorides R4-COCl with the N-trimethylsilylenamines 3.The compounds 3 are obtained from the regioselective N-silylation (yields 60-98percent) of the lithioenamines 2, which result from the condensation of nitriles R3-CN having no alpha-hydrogen atom with 2-lithiomethyl derivatives of s-collidine, 2,4-lutidine and 2,4-dimethylquinoline.

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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 oxidative degradation of aqueous, concentrated 2-amino-2-methyl-1- propanol (AMP)/monoethanolamine (MEA) mixture has been investigated in batch reactors at temperatures in the range of 100-140C, and oxygen pressures in the range of 250-350 kPa. The oxidation pathway of individual AMP was proposed before attempting to investigate the oxidation of AMP/MEA blend. As compared with degradation of single MEA and AMP, no cross product was found in the degraded AMP/MEA blend under the experimental conditions. This result showed that AMP and MEA could be oxidized in parallel in the mixture. Both the overall degradation rates of MEA and AMP increased with raising temperature and oxygen partial pressure. MEA degraded faster than AMP in the blend under all the experimental conditions. The degradation rate of AMP decreased indicating MEA protects AMP from oxidation in the mixture when initial MEA concentration was increased.

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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