Properties and Exciting Facts About (1R,2R)-Cyclohexane-1,2-diamine

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Aliphatic Amines: A Critical Analysis of the Experimental Enthalpies of Formation by Comparison with Theoretical Calculations

The accuracy of experimental data on enthalpies of formation and vaporization of aliphatic amines (primary, secondary, and tertiary amines, di-, tri-, and tetramines, and cycloalkylamines) was assessed by theoretical calculations. The gas-phase enthalpies of formation were calculated using the Gaussian 4 (G4) method combined with isodesmic reactions. Three amines, CH3NH2, CH3NHCH3, and (CH3)3N, were used as the main reference species in the isodesmic reactions; their experimental enthalpies of formation were recently revisited in the Active Thermochemical Tables. The enthalpies of vaporization were estimated by three group additivity and molecular electrostatic potential models and then were used to calculate the enthalpies of formation in the liquid state. When the deviations of experimental values from those provided by the theoretical methods were analyzed, a set of accurate and consistent values of enthalpy of formation of aliphatic amines was recommended for use in thermochemical calculations and as benchmarks for theoretical chemistry.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Synthesis of novel enantiomerically pure trianglimine and trianglamine macrocycles

The synthesis of a series trianglimine macrocycles is described using a [3+3] cyclocondensation strategy between a 1,2-diamine and an aromatic dicarboxaldehyde. The novel compounds have been prepared in enantiomerically pure form and their ring sizes range from 30 to 42.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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NOVEL LACTAM COMPOUND

The present invention provides a novel lactam compound, a sugar transport enhancement agent containing this compound as an active ingredient, an agent for the prevention and/or treatment of diabetes mellitus, diabetic peripheral neuropathy, diabetic nephropathy, diabetic retinopathy, diabetic macrovascular disease, glucose tolerance anomaly, obesity and the like. In addition, the present invention also provides a preparation method for the novel lactam compound, and a preparation intermediate thereof.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Discovery of (1R,2R)-Cyclohexane-1,2-diamine

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Weak absolute helicity direction in Ni-salen by trans-cyclohexane-(1R,2R)- diamine

Helical Ni-salen foldamers were synthesized from enantiomerically pure cyclohexane-(1R,2R)-diamine, N,N?-bis-(N-phenyl (4-diphenylphosphine)-3- salicylidenato carboxamide)-(1R,2R)-cyclohexanediaminato-nickel(II). X-ray structural characterization of the absolute helicities observed confirms our earlier assertions, based on solution spectroscopic evidence, that trans-cyclohexane-diamine, a common component of chiral salen catalysts, is a weak director of absolute helicity for Ni-salen.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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SINTESIS, ESTUDIO DINAMICO POR RMN Y CALCULOS TEORICOS DE HEXAHIDRO- Y TETRAHIDROQUINOXALINAS 2,3-DISUSTITUIDAS

The synthesis of 2,3-disubstituted hexahydroquinoxaline stereoisomers from 1,2-diaminocyclohexanes and the corresponding alpha-dicarbonylic derivatives and their oxidation to tetrahydroquinoxalines is described.Their 1H- and 13C-NMR spectra are analyzed and a 13C-DNMR study on cis 2,3-diphenyl-hexahydroquinoxaline 1a is carried out.The DeltaH*, DeltaS* and DeltaG* for the dynamic process of interchange between the two chair conformers of cis 1a are calculated.A theoretical study, using the semiempirical methods AM1 and PM3 of cis and trans 1a, as well as Ab initiocalculations, using 4-31G basis over optimized geometries by the semiempiric method PM3, of their analogues without phenyl substituents are reported.The DeltaH* values calculated are in agreement with the experimental value of cis 1a.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

The important role of (1R,2R)-Cyclohexane-1,2-diamine

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Towards new imidazole-2-thione-based organocatalysts; Sulfur transfer vs. deoxygenation in the reaction of imidazole N-oxides and cycloaliphatic thioketones

Sulfuration or deoxygenation? Competitive transformations of the title imidazole N-oxides into respective masked thiourea analogs or into the parent heterocycle in the reaction with 2,2,4,4-tetramethylcyclobutane-1,3-dithione are presented. The influence of an electron-withdrawing substituents in combination with the steric hindrance of neighboring groups onto reaction outcome is discussed.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Two chiral coordination polymers constructed from (1R,2R)-1,2-diaminocyclohexane derivative: Syntheses, structures and properties

Two chiral coordination polymers were synthesized by using a chiral ligand (1R,2R)-1,2-bis(4-(1,2,4-triazolyl))cyclohexane to assemble with Zn(II)/Ag(I) salts. The different coordination modes of the ligand result in two diverse structures, such as a 0D structure for 1 and a 1D chain for 2, respectively. The chiral nature of compounds 1 and 2 was confirmed by circular dichroism spectra (CD) and second harmonic generation (SHG) efficiency measurements. Furthermore, the photoluminescent properties of compounds 1 and 2 have been investigated in the solid state at ambient temperature.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, Application In Synthesis of (1R,2R)-Cyclohexane-1,2-diamine, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 20439-47-8, Name is (1R,2R)-Cyclohexane-1,2-diamine, molecular formula is C6H14N2. In a Article, authors is Bravin, Carlo£¬once mentioned of 20439-47-8

Binding Profiles of Self-Assembled Supramolecular Cages from ESI-MS Based Methodology

Confined molecular environments have peculiar characteristics that make their properties unique in the field of biological and chemical sciences. In recent years, advances in supramolecular capsule and cage synthesis have presented the possibility to interpret the principles behind their self-assembly and functions, which has led to new molecular systems that display outstanding properties in molecular recognition and catalysis. Herein, we report a rapid method based on ESI-MS to determine the binding profiles for linear saturated dicarboxylic acids in a series of different cages. The cages were obtained by self-assembly of modified tris(pyridylmethyl)amine (TPMA) complexes and diamines chosen to explore variations in their size and flexibility. This methodology has provided information on how small changes in the structures of the host and guest can contribute to recognition events. Moreover, it was possible to study molecular systems that contain paramagnetic metals, which are not suitable for classical binding-constant determination by 1H NMR spectroscopy.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chiral manganese(III) salen catalysts immobilized on MCM-41 and delaminated zeolites ITQ-2 and ITQ-6 through new axial coordinating linkers

We report that the catalytic behavior and enantioselectivity of three different chiral Mn(III) salen complexes anchored to traditional supports such as MCM-41 (38-A pore diameter) and delaminated zeolitic materials ITQ-2 and ITQ-6 strongly depend on whether the complexes are attached to the surfaces through the chiral equatorial tetradentate salen ligand or via the apical ligand. As for the case of unsupported complexes, this experimental observation has been accounted for strong variations in the conformational preference of the catalyst intermediate toward the approaching olefin, as well as to unfavorable structural changes in the complex. In addition, control of the hydrophobicity of the surface allows for optimization of selectivity in obtaining chiral epoxides.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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X-Ray Structural Studies of Highly Enantioselective Mn(salen) Epoxidation Catalysts

The relationship between catalyst structure and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins by a series of chiral Mn(salen) complexes (1-10) was examined.The X-ray structures of 5-coordinate complexes 5, 8, of 6-coordinate 9 (<6,6' = -tBu; 4,4' = -tBu>+ClO4-), and 10 (6,6′ = -tBu; 4,4′ = -Br) were determined.Catalysts 1-9 were derived from (R,R)-1,2-diaminocyclohexane and catalysts 10 from (S,S)-1,2-diphenylethylenediamine.Catalysts 1-9 differ in the stereoelectronic substitution of the ortho (6,6′) and para (4,4′) positions of the salicylidene moiety.A comparison between structures 5, 8, and 9 reveals that the ligand geometry around the metal cnter and the chiral diimine backbone remains remarkably constant in both five- and six-coordinate cyclohexanediamine-derived complexes; in contrast, the salicylidene regions of the complexes display a wide range of conformations.The asymmetric epoxidation of indene and 6-cyano-2,2-dimethylchromene with NaOCl catalyzed by complexes 1-10 was effected.Systematically increasing the steric bulk on the ortho and then the para position in the order 1 (6,6′ = -H; 4,4′ = -H), 2 (6,6′ = -CH3; 4,4′ = -CH3), 3 (6,6′ = -tBu; 4,4′ = -H), 4 (6,6′ = -tBu; 4,4′ = -CH3), 5 (6,6′ = -tBu; 4,4′ = -tBu), and 6 (6,6′ = -tBu; 4,4′ = -trityl), and electronically modifying the para substituents in 7 (6,6′ = -tBu; 4,4′ = -OMe) and 8 (6,6′ = -tBu; 4,4′ = -OTIPS) resulted in enhanced enantioselectivities of the desired epoxides.The conformational variations observed in the solid state are likely to reflect accessible solution conformations and may help explain the high levels of stereoinduction obtained with these catalysts in the asymmetric epoxidation of unfunctionalized olefins. – Keywords: asymmetric epoxidations; catalysis; manganese complexes; structure elucidation

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI