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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

The important role of 3,4-Di(1H-indol-3-yl)-1H-pyrrole-2,5-dione

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Several members of the Cryptophycin family were synthesised using a straightforward convergent approach. The proposed synthetic route was used to prepare novel analogs of Cryptophycins A and B in which the benzylic epoxide moiety was replaced by alternate electrophilic functions. The effect of these modifications on cytotoxic activity was determined on several tumor cell lines.

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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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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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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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A small library of ninety four uridine antibiotic analogs was synthesized, under the Pilot Scale Library (PSL) Program of the NIH Roadmap initiative, from amine 2 and carboxylic acids 33 and 77 in solution-phase fashion. Diverse aldehyde, sulfonyl chloride, and carboxylic acid reactant sets were condensed to 2, leading after acid-mediated hydrolysis, to the targeted compounds 3-32 in good yields and high purity. Similarly, treatment of 33 with diverse amines and sulfonamides gave 34-75. The coupling of the amino terminus of d-phenylalanine methyl ester to the free 5?-carboxylic acid moiety of 33 followed by sodium hydroxide treatment led to carboxylic acid analog 77. Hydrolysis of this material gave analog 78. The intermediate 77 served as the precursor for the preparation of novel dipeptidyl uridine analogs 79-99 through peptide coupling reactions to diverse amine reactants. None of the described compounds show significant anticancer or antimalarial acivity. A number of samples exhibited a variety of promising inhibitory, agonist, antagonist, or activator properties with enzymes and receptors in primary screens supplied and reported through the NIH MLPCN program.

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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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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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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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Three adducts of zinc azide with 2,4-/3,4- and 3,5-dimethylpyridine (DMP), respectively, were prepared and the crystal structures determined by single crystal X-ray diffraction methods.The three compounds crystallize in the monoclinic space group P21/c with Z = 4: Zn(N3)2*2,4-DMP at 300(2) K: a = 1098.6(4), b = 1600.2(6), c = 608.8(3) pm, beta = 102.47(3) deg; R = 0.071 (RW = 0.056).Zn(N3)2*3,4-DMP at 103(3) K: a = 1102.1(3), b = 1.649.0(4), c = 611.8(1) pm, beta = 104.54(2) deg; R = 0.055 (RW = 0.051).Zn(N3)2*3,5-DMP at 97(3) K: a = 602.1(2), b = 2037.9(7), c = 853.8(3) pm, beta = 90.77(3) deg; R = 0.069 (RW = 0.055).The molecular geometry is similar for the three adducts, but the packing of the DMP-molecules is different.The zinc atoms are surrounded by five nitrogen atoms, four belonging to the azide groups and one to the DMP-adduct.The trigonal bipyramidal shaped ZnN5-polyhedra share common edges to form chains.Keywords.Azide; Crystal structure; Dimethylpyridine; Zinc.

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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