Archives for Chemistry Experiments of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Asymmetric hydrogenation of ketones catalyzed by a ruthenium(ii)-indan- ambox complex

(S,R)-Indan-ambox ligand and its ruthenium(ii) complex have been prepared and successfully applied to asymmetric hydrogenation of prochiral simple ketones. A wide range of unfunctionalized ketones are reduced by Ru(ii)-indan-ambox catalyst with excellent enantioselectivities (up to 97% ee).

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Application of dimedone enamines as dienophiles: stereoselective synthesis of amino enols of fused uracils containing a sugar moiety by hetero-Diels-Alder reactions of barbituric acid 5-ylidene alditols with dimedone enamines

Dimedone enamines were applied for the first time as new dienophiles in hetero-Diels-Alder reactions with inverse electron demand. Cycloadditions of barbituric acid 5-ylidene alditols with dimedone enamines were performed in dichloromethane at room temperature for 3 days and fused uracils-chromeno[2,3-d]pyrimidine-2,4-diones were obtained in good 73-87% yields. Only one enantiomerically pure stereoisomer was obtained in each studied cycloaddition. Analysis of 1H NMR and 2D NMR spectra allowed for the determination that cycloadducts exist in solution as mixture of the neutral form and dipolar ion. The prepared fused uracils contain both amine and enol functional groups, so share amphiprotic properties and they are zwitterions in solid state. The new class of compounds-amino enols was synthesized, which similarly to amino acids exists as zwitterions. In obtained cycloadducts amino groups and sugar moieties are close each other and they both are in cis configuration and in axial position. It was also shown that different alkenes can be used as dienophiles towards barbituric acid 5-ylidene alditols, for example, styrene or 1-amino-2-thiocarbamoyl-cyclopent-1-ene.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Discovery of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Gamma-hydroxy-2-(fluoroalkylaminocarbonyl)-1-piperazinepentanamides and uses thereof

gamma-Hydroxy-2-(fluoroalkylaminocarbonyl)-1-piperazinepentanamide compounds are inhibitors of HIV protease and inhibitors of HIV replication. These compounds are useful in the prevention or treatment of infection by HV and the treatment of AIDS, either as compounds, pharmaceutically acceptable salts, pharmaceutical composition ingredients, whether or not in combination with other antivirals, immunomodulators, antibiotics or vaccines. Methods of treating AIDS and methods of preventing or treating infection by HIV are also described. These compounds are effective against HIV viral mutants which are resistant to HIV protease inhibitors currently used for treating AIDS and HIV infection.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Extended knowledge of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Highly stereoselective asymmetric 6pi-azaelectrocyclization utilizing the novel 7-alkyl substituted cis-1-amino-2-indanols: Formal synthesis of 20-epiuleine

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£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Molecular characterization of alkyl nitrates in atmospheric aerosols by ion mobility mass spectrometry

We demonstrate the capability of the ion mobility mass spectrometry (IMS-MS) for molecular characterization of reactive and short-lived alkyl nitrates (ANs) in atmospheric aerosols. We show significantly enhanced sensitivity towards the intact molecules of ANs by ultimately 2 orders of magnitude with the addition of inorganic anions such as chloride and nitrate to the negative electrospray to promote the ion adduct formation. This approach enables the measurement of ANs that have a low tendency to form molecular ions on their own with an improved limit of detection in the range of 0.1 to 4.3muM. Molecular identities of the ANs are well constrained by the developed correlation between the collision cross section and mass-to-charge ratio, which provides a two-dimensional separation of the ONO2-containing compounds on the basis of their molecular size and geometry. Structural information of the nitrate molecules is further probed by the identification of characteristic fragments produced from the collision-induced dissociation of parent AN adducts. Application of the IMS-MS technique is exemplified by the identification of hydroxy nitrates in secondary organic aerosols produced from the photochemical oxidation of isoprene.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The cis-influence of hydroporphyrin macrocycles on the axial ligation equilibria of cobalt(II) and zinc(II) porphyrin complexes

Stability constants and thermodynamic data are reported for coordination of piperidine, pyridine, and substituted pyridines to the cobalt(II) and zinc(II) complexes of octaethylporphyrin (OEP), t-octaethylchlorin (OEC) and the tct-and ttt-isomers of octaethylisobacteriochlorin (OEiBC) in toluene, cyclohexane, and chloroform solution at 25.0 C. Under the conditions of the study, only 1:1 complexes are formed. With the exception of the case of 2-substituted pyridines, the stability constants, log K, correlate roughly with the base strength of the nitrogenous ligand but correlate closely with the log K for coordination of the base to Zn(OEP). A cis-influence of the macrocycle saturation level on the stability constants is observed. Stability constants for coordination of a given ligand to OEiBC complexes are typically 4 times greater than those for coordination to OEP complexes and 1.8 times greater than those for coordination to OEC complexes. The stability constants of both Co- and Zn(OEiBC) complexes were unaffected by the stereochemistry (tct vs ttt) of the ethyl substituents, unlike the case for nickel. DeltaH and DeltaS vary between -8 and -12 kcal/mol and -12 and -24 cal K-1 mol-1, respectively, and correlate linearly with each other. They do not correlate directly with either log K or the saturation level of the macrocycle. For most bases, log K is greater for the zinc complexes than for the cobalt complexes. However, for 3,5-dichloropyridine, log K is greater for the cobalt complexes. The acid dissociation constants for the free-base compounds H2(OEP), H2(OEC), and H2(OEiBC) were measured in THF/n-butanol solution. All three compounds ionize to dianions by simultaneous loss of two protons. OEP and OEiBC have pKa = 15.9. OEC is a weaker acid with pKa = 16.6. The increase in log K with macrocycle saturation level does not correlate with the acidity of the respective free bases, but the latter is not necessarily representative of the sigma-donor strength of the macrocycle dianion. Solvation and pi-effects are not responsible for either the dependence of log K on macrocycle saturation level or the reversal for weak bases of the relative Lewis acid strengths of the cobalt and zinc complexes. The latter is attributed to a relief of strain due to core expansion that occurs upon ligand coordination to cobalt complexes. Cobalt complexes are more sensitive than zinc complexes to steric interactions with the ortho-substituents of a pyridine ligand owing to the much smaller out-of-plane displacement of the cobalt atom compared to the zinc atom in five-coordinate complexes.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Analogues of sparteine. 5. Antiarrhythmic activity of selected N,N’-disubstituted bispidines

A series of seven N,N’-disubstituted bispidines, structurally analogous to the inner (B and C) rings of sparteine (1) and encompassing a range of lipophilicity in which 1 was centered, has been compared to 1 in regard to antiarrhythmic potency and acute toxicity. Several of the bispidines were of comparable potency, and all but one were somewhat less toxic than 1. The ability of the mononitrate salts of 1 and bispidines 6 and 7 to bind calcium and magnesium cations in Me2So-d6 solvent has been evaluated by proton magnetic resonance analysis. No binding could be demonstrated under these conditions, which suggested that pharmacologic effects of these compounds may be due to properties other than direct binding of these cations.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Hydroxymethylation of Quinolines with Na2S2O8 by a Radical Pathway

Quinolines and isoquinolines were treated with Na2S2O8 in a mixture of methanol and water at 70 C to form hydroxymethylated quinolines and isoquinolines in good to moderate yields, under transition-metal-free conditions. The formed hydroxymethyl group was smoothly converted into aldehyde, ester, amide, bromomethyl, (N,N-diethylamino)methyl, cyano, and tetrazole groups, in good yields.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Development of bifunctional aza-bis(oxazoline) copper catalysts for enantioselective henry reaction

Base-functionalized aza-bis(oxazoline) ligands were prepared to explore the concept of dual activation through the Lewis acid and a tethered tertiary amine base. The catalytic activity of the Cu complex was evaluated for the asymmetric Henry reaction. Compared with a corresponding unfunctionalized copper complex with external 1-benzyl-4-ethylpiperazine base, the ethylpiperazine- functionalized aza-bis(oxazoline) copper catalyst resulted in rate acceleration (2.5 times) as well as improved enantioselectivity (72% ee vs 92% ee).

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Total synthesis of (-)-lycoposerramine-S

To the core: The first total synthesis of (-)-lycoposerramine-S has been accomplished in 14 steps. The synthesis features the facile construction of the tetracyclic core through an intramolecular 1,3-dipolar cycloaddition of an azomethine ylide, with unexpected stereoselectivity, an 5-exo-trig radical cyclization, and an alkylation of p-nosyl (Ns) amide. TBS=tert- butyldimethylsilyl. Copyright

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis