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The use of phosphogypsum, which is a waste product of the phosphorus fertilizer industry, as a heterogeneous catalyst in condensation of acetylacetone, acetylene, and ammonia is considered.

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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 13C NMR spectra of 22 alkyl-substituted 9aH-quinolizine-1,2,3,4-tetracarboxylates have been obtained and X-ray analyses have been performed for three of them.The chemical shift differences between the parent 9aH-quinolizine and the methyl-substituted compounds can only be interpreted in terms of the usual alpha and beta effects for 8-methyl-9aH-quinolizine. 6-, 7-, 9-, and 9a-methyl substituents cause not only a very large deshielding of the carbon at the position of substitution together with shielding changes at adjacent atoms, but also influence the shieldings of the other carbons in both rings of the compounds under study.The observed changes are interpreted in terms of steric hindrance between the methyl groups of ring B and the ester groups of ring A, and hyperconjugative effects introduced by the 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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A novel class of therapeutic drug candidates for heart failure, highly potent and selective GRK2 inhibitors, exhibit potentiation of beta-adrenergic signaling in vitro studies. Hydrazone derivative 5 and 1,2,4-triazole derivative 24a were identified as hit compounds by HTS. New scaffold generation and SAR studies of all parts resulted in a 4-methyl-1,2,4-triazole derivative with an N-benzylcarboxamide moiety with highly potent activity toward GRK2 and selectivity over other kinases. In terms of subtype selectivity, these compounds showed enough selectivity against GRK1, 5, 6, and 7 with almost equipotent inhibition to GRK3. Our medicinal chemistry efforts led to the discovery of 115h (GRK2 IC50 = 18 nM), which was obtained the cocrystal structure with human GRK2 and an inhibitor of GRK2 that potentiates beta-adrenergic receptor (betaAR)-mediated cAMP accumulation and prevents internalization of betaARs in beta2AR-expressing HEK293 cells treated with isoproterenol. Therefore, 115h appears to be a novel class of therapeutic for heart failure treatment.

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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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Diethyl 2,3-dihydro-6-azaindoline-2,5-dicarboxylate 4b was synthesized and used as starting material in the preparation of a novel benzodiazepine-beta-carboline type hybrid molecule (3aR,S)-ethyl 3,10-dioxo-2,3,3a,4-tetrahydro-10H-pyrido<3',4':5,4>pyrrolo<1,2-c><1,4>-benzodiazepine-6-carboxylate 5b.The benzodiazepine receptor binding affinities of this compound and its precursors were found to be very modest in vitro.These results confirm our previously proposed model of the configuration of the benzodiazepine and beta-carboline binding sites on the receptor as represented by the configuration of these two moieties in the high affinity hybrid 3.

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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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Conditions for chemical assembly of new heterometallic trinuclear pivalates [Cd2M(piv)6L2] (M = Mg, Ca, or Sr; piv is pivalate) were found. Reactions with the nonchelating ligand 2,4-lutidine (lut) gave the crystals of heterometallic complexes [Cd2M(piv)6(lut)2] (M = Mg (1), Ca (2), and Sr (3)). With the chelating ligand 1,10-phenanthroline (phen), only the homometallic dimer [Cd2(piv)4(phen)2] (4) was obtained under these conditions. Yet heterometallic trinuclear complexes with 1,10-phenanthroline ([Cd2Mg(piv)6(H2O)(phen)2] (5), [CaCd2(piv)6(phen)2] (6), and [Cd2Sr(piv)6(phen)2]?2MeCN (7)) were synthesized by reactions of phen with complexes 1?3. For all the complexes obtained, the molecular and crystal structures as well as the details of their molecular architecture were determined. The thermal behavior of aqua complex 5 was studied by TG and DSC. The complex eliminated the water molecule between 130 and 180 C with a high endothermic effect (Q = 101 kJ mol?1) due to (1) intramolecular hydrogen bonds that stabilize its molecular architecture and (2) subsequent structural rearrangements.

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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 novel 7-amino-6-hetarylimidazolo[1,2-a]pyrimidine compounds of formula (I), the salts thereof, the use of said compounds for controlling harmful fungi, and agricultural pesticides containing at least one such compound as an active component. The substituents Het, X, Y1, and Y2 in formula (I) have the following meanings: Het represents a five-membered or six-membered heteroaromatic radical which can contain one, two, three, or four heteroatoms selected among O, S, and N as ring members, said five-membered or six-membered heteroaromatic radical being optionally provided with one, two, three, or four identical or different substituents L; X represents hydrogen, OH, halogen, cyano, NR3R4, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, C2-C8 alkenyl, or C2-C8 alkinyl, the seven latter radicals being optionally halogenated in full or in part and/or optionally carrying one, two, or three substituents selected among nitro, cyano, C1-C2 alkoxy, C1-C4 alkoxycarbonyl, amino, C1-C4 alkylamino, and di-C1-C4 alkylamino. R3 and R4 independently have the meanings indicated for R1 or R2; Y1, Y2 independently represent hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkyl halide, C3-C7 cycloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C1-C4 haloalkoxy; and R1, R2 have the meanings indicated in the claims and the description.

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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 family of iron complexes with general formula [Fe(II)( R,Y,XPyTACN)(CF3SO3)2], where R,Y,XPyTACN=1-[2?-(4-Y-6-X-pyridyl)methyl]-4,7-dialkyl-1,4, 7-triazacyclononane, X and Y refer to the groups at positions 4 and 6 of the pyridine, respectively, and R refers to the alkyl substitution at N-4 and N-7 of the triazacyclononane ring, are shown to be catalysts for efficient and selective alkene oxidation (epoxidation and cis-dihydroxylation) employing hydrogen peroxide as oxidant. Complex [Fe(II)(Me,Me,HPyTACN)(CF 3SO3)2] (7), was identified as the most efficient and selective cis-dihydroxylation catalyst among the family. The high activity of 7 allows the oxidation of alkenes to proceed rapidly (30 min) at room temperature and under conditions where the olefin is not used in large amounts but instead is the limiting reagent. In the presence of 3 mol% of 7, 2 equiv. of H2O2 as oxidant and 15 equiv. of water, in acetonitrile solution, alkenes are cis-dihydroxylated reaching yields that might be interesting for synthetic purposes. Competition experiments show that 7 exhibits preferential selectivity towards the oxidation of cis olefins over the trans analogues, and also affords better yields and high [syn-diol]/[epoxide] ratios when cis olefins are oxidized. For aliphatic substrates, reaction yields attained with the present system compare favourably with state of the art Fe-catalyzed cis-dihydroxylation systems, and it can be regarded as an attractive complement to the iron and manganese systems described recently and which show optimum activity against electron-deficient and aromatic olefins. 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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Bispidines (3,7-diazabicyclo[3.3.1]nonanes) as very rigid and highly preorganized ligands find broad application in the field of coordination chemistry, and the redox potentials of their transition-metal complexes are of importance in oxidation reactions by high-valent iron complexes, aziridination catalyzed by copper complexes, and imaging by 64Cu positron emission tomography tracers. Here, we show that the redox potentials and stability constants of the copper(II) complexes of 15 tetradentate bispidines can be varied by substitution of the pyridine rings (variation of the redox potential over ca. 450 mV and of the complex stability over approximately 10 log units). It is also shown that these variations are predictable by the pKa values of the pyridine groups as well as by the Hammett parameters of the substituents, and the density functional theory based energy decomposition analysis also allows one to accurately predict the redox potentials and concomitant complex stability. It is shown that the main contribution emerges from the electrostatic interaction energy, and the partial charges of the pyridine donor groups therefore also correlate with the redox potentials.

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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 ambient and high-pressure stopped-flow kinetic study of the halogen-bridge cleavage reaction in the pallada- and platina-cycles <2> (M = Pd or Pt; R = H, 4-MeO, 5-Me or 5-F; X = Cl or I) by a series of substituted pyridines in chloroform as solvent revealed that it is a fast, associatively driven second-order process, with strong steric rather than electronic demands.Substituent effects and activation parameters (DeltaH(excit.),DeltaS(excit.) and DeltaV(excit.)) were in full accord with the proposed associative mechanism.The Pd dimers transformed into N,N-trans monomers of the type (py = pyridine).In contrast, the Pt counterparts afford N,N-cis species under the same conditions.The geometry of the N,N-cis complex X(py)>, as well as of the N,N-trans platinacycle Cl(py)>, has been confirmed by X-ray crystallography.The most striking structural differences in the N,N-cis and N,N-trans related platinacycles are the Pt-Cl and Pt-N(py) bond distances <2.300(1) and 2.408(5), 2.138(4) and 2.02(1) Angstroem, respectively>.The crystal structure of trans-<(n-Bu3P)IPd(mu-I)2PdI(P-n-Bu3)> has also been determined and used to account for its similar reactivity to <2> in the bridge-splitting reaction.

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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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gamma-Ray irradiation of a binary solution consisting of pyridine and methanol caused almost no reaction of pyridine.However, the addition of a catalytic amount of nickel nitrate to this binary solution induced the alpha-methylation of pyridine in good yield upon gamma-ray irradiation at room temperature either in air or in vacuo.This alpha-methylation gave alpha-picoline as a major product.The yield of alpha-picoline increased with increase in the irradiation time at the initial stage of the reaction, reached a maximum (27.8percent) at an irradiation duration of between 8 and 10h, and then decreased progressively at greater irradiation times.In addition, the yield of alpha-picoline at a given irradiation time showed a tendency to increase with increasing amount of the nickel nitrate catalyst or with increasing fraction of methanol in the starting solution. gamma-Ray irradiation in the presence of nickel nitrate was also found to induce the catalytic alpha-methylation of gamma-picoline with methanol at room temperature either in air or in vacuo, giving 2,4-lutidine as a major product in a maximum yield of 8.3percent.Further, the demethylation reaction of alpha-picoline to pyridine and that of 2,4-lutidine to gamma-picoline were also promoted greatly upon gamma-ray irradiation at room temperature in air in the presence of both methanol and nickel nitrate.

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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