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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:
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 unprecedented diaza-ene reaction of formaldehyde N-tert-butyl hydrazone with nitroalkenes can be efficiently catalyzed by an axially chiral bis-thiourea to afford the corresponding diazenes in good to excellent yields (60-96%) and moderate enantioselectivities, up to 84 : 16 er; additional transformation of diazenes into their tautomeric hydrazones proved to be operationally simple and high-yielding, affording bifunctional compounds which represent useful intermediates for the synthesis of enantioenriched beta-nitro-nitriles and derivatives thereof.

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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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Disclosed herein are substituted diphenylmethyl picolinic acids, pharmaceutically acceptable salts, amides and esters thereof. The compounds disclosed are useful as topical anti-acne agents.

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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 chiral anthracenecarboxylic acid/amine supramolecular organic fluorophore composed of a 2D layered network structure was developed by combining 1-amino-2-indanol and 2-anthracenecarboxylic acid molecules. This 2D, chiral fluorophore exhibits circularly polarized luminescence (CPL) without quenching the fluorescence in the solid state.

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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

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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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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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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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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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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