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Enantioseparations by gas chromatography using porous organic cages as stationary phase

The resolution of chiral compounds into optically pure enantiomers is very important in various fields, such as pharmaceutical, chemical, agricultural, and food industries. Chiral gas chromatography (GC) is one of the efficient methods for enantioseparations of volatile compounds. In recent years, porous materials as stationary phases for chromatographic separations have achieved increasing attention. Porous organic cages (POCs) represent an emerging class of porous materials, which are assembled by discrete organic molecules with shape-persistent and permanent cavities through weak intermolecular forces. This chapter describes several chiral POCs as chiral stationary phases for GC enantioseparations of racemic compounds.

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

Extended knowledge of (1R,2R)-Cyclohexane-1,2-diamine

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Highly enantioselective aldol reactions using a tropos dibenz[c,e]azepine organocatalyst

The four-step synthesis of a chiral primary tertiary diamine salt, possessing a tropos dibenz[c,e]azepine ring is described. It is shown that 3.5-5 mol % of this salt is capable of promoting highly enantioselective crossed-aldol reactions between cyclohexanone and a series of aromatic aldehydes. In all cases, the aldol reactions proceed with high diastereoselectivity for the anti-aldol product. The outcome of crossed-aldol reactions involving other cyclic ketones and acyclic ketones are also described. All examples involving cyclic ketones result in selectivity for the anti-aldol products, whereas acyclic ketones were found to favour the syn-aldol products. A discussion on the role of the chiral primary tertiary diamine salt in the catalysis of the aldol reactions is also presented.

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

Extracurricular laboratory:new discovery of (1R,2R)-Cyclohexane-1,2-diamine

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An enantiomerically pure schiff base ligand

(1R,2K)-(-)-N,N?-Bis(quinoline-2-methylidene)-1,2-cyclohexanediamine, C26H24N4, was prepared by the reaction of quinoline-2-carbaldehyde and the corresponding diamine. The crystal structure of the resulting enantiomerically pure quadridentate ligand has been determined.

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

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Cu-catalyzed selective mono-N-pyridylation: Direct access to 2-aminoDMAP/sulfonamides as bifunctional organocatalysts

Direct and selective mono-N-pyridylation of trans-(R,R)-cyclohexane-1,2- diamine is described here. Facile preparation of a novel chiral 2-aminoDMAP core catalaphore via Cu catalysis has led to the development of various sulfonamide/2-aminoDMAPs as bifunctional acid/base organocatalysts (most in two steps overall), which have been shown to very effectively promote asymmetric conjugate addition of acetylacetone to trans-beta-nitroolefins with good to excellent yields (87-93%) and enantioselectivites (up to 99%).

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

Archives for Chemistry Experiments of (1R,2R)-Cyclohexane-1,2-diamine

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Temperature-controlled polymorphism of chiral CuII-LnIII dinuclear complexes exhibiting slow magnetic relaxation

A new family of 3d-4f dinuclear complexes derived from a chiral Schiff-base ligand, (R,R)-N,N?-bis(3-methoxysalicylidene)cyclohexane-1,2-diamine (H2L), has been synthesized and structurally characterized, namely, [Cu(L)Ln(NO3)3(H2O)] (Ln = Ce (1) and Nd (2)), [Cu(L)Sm(NO3)3]¡¤2CH3CN (3) and [Cu(L)Ln(NO3)3] (Ln = Eu (4), Gd (5 and 5?), Tb (6 and 6?), Dy (7 and 7?), Ho (8), Er (9) and Yb (10)). Structural determination revealed that these complexes are composed of two diphenoxo-bridged CuII-LnIII dinuclear clusters with slight structural differences. Complexes 1, 2 and 4-7 crystallize in the chiral space group P1, and the space group of 3 is P21, while the other six complexes (5?-7? and 8-10) are isomorphous and each of them contains two slightly different CuII-LnIII dinuclear clusters in the asymmetric unit with the chiral space group P21. Magnetic investigations showed that ferromagnetic couplings between the CuII and LnIII ions exist in 5-7 and 5?-7?. Moreover, the alternating current (ac) magnetic susceptibilities of 6, 6?, 7 and 7? showed that both the in-phase (chi?) and out-of-phase (chi??) are frequency- and temperature-dependent with a series of frequency-dependent peaks for the chi??, which being typical features of field-induced slow magnetic relaxation phenomena. For 8, a frequency dependent chi? with peaks but chi?? without peaks appeared; however, the compound displays field-induced slow magnetic relaxation behavior. Furthermore, no obvious frequency-dependent ac signal was observed in 9 owing to the absence of the easy-axis anisotropy. More significantly, we observed the temperature-controlled reversible conversion from one chiral single-crystal (5-7) to another chiral single-crystal (5?-7?) exhibiting slow magnetic relaxation.

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

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Probing the mechanism and dynamic reversibility of trianglimine formation using real-time electrospray ionization time-of-flight mass spectrometry

RATIONALE The [3+3]-cyclocondensation reactions of chiral (1R,2R)-1,2-diaminocyclohexane with aromatic or aliphatic bis-aldehydes to form trianglimine macrocycles were reported a decade ago and were believed to proceed through a stepwise mechanistic pathway; however, no intermediates were ever isolated or detected and characterized. METHODS We investigated the mechanism of the [3+3]-cyclocondensation reaction using a selection of dialdehyde starting materials using real-time electrospray ionization time-of-flight mass spectrometry. RESULTS We observed up to a maximum of 16 reaction intermediates along the reaction pathway, more than for any other multistep reaction reported. We also probed the dynamic reversibility of trianglimines using selected small dynamic combinatorial libraries and showed that trianglimine formation is indeed fully reversible. CONCLUSIONS This study represents a significant contribution towards understanding the mechanism of trianglimine formation and its potential applicability can be extended to include other cascade reactions.

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

Some scientific research about (1R,2R)-Cyclohexane-1,2-diamine

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Stoichiometry-controlled supramolecular chirality induction and inversion in bisporphyrin systems

Chemical equation presented Stoichiometry is found to be an effective tool for controlling supramolecular chirality induction and inversion processes. Chirality induction in the achiral syn ethane-bridged bis(zinc octaethylporphyrin) is achieved upon interaction with the enantiopure (R,R)-1,2-diphenylethylenediamine at the low molar excess region, to yield the right-handed chiral 1:1 tweezer complex. Further increase of the ligand concentration results in chirality inversion as the equilibrium shifts toward the extended left-handed 1:2 anti complex as a result of switching of the complex helicity.

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

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

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Enantioselective sensing of amines based on [1 + 1]-, [2 + 2]-, and [1 + 2]-condensation with fluxional arylacetylene-derived dialdehydes

Four induced circular dichroism (ICD) probes exhibiting a stereodynamic arylacetylene framework and terminal aldehyde units have been prepared. The CD silent sensors generate a strong chiroptical response to substrate-controlled induction of axial chirality upon selective [1 + 1]-, [2 + 2]-, and [1 + 2]-condensation. The intense Cotton effects can be exploited for in situ ICD analysis of the absolute configuration and ee of a wide range of amines.

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

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Approaching the Kinetic Inertness of Macrocyclic Gadolinium(III)-Based MRI Contrast Agents with Highly Rigid Open-Chain Derivatives

A highly rigid open-chain octadentate ligand (H4cddadpa) containing a diaminocylohexane unit to replace the ethylenediamine bridge of 6,6?-[(ethane-1,2 diylbis{(carboxymethyl)azanediyl})bis(methylene)]dipicolinic acid (H4octapa) was synthesized. This structural modification improves the thermodynamic stability of the Gd3+ complex slightly (log KGdL=20.68 vs. 20.23 for [Gd(octapa)]-) while other MRI-relevant parameters remain unaffected (one coordinated water molecule; relaxivity r1=5.73 mm-1 s-1 at 20 MHz and 295 K). Kinetic inertness is improved by the rigidifying effect of the diaminocylohexane unit in the ligand skeleton (half-life of dissociation for physiological conditions is 6 orders of magnitude higher for [Gd(cddadpa)]- (t1/2=1.49¡Á105 h) than for [Gd(octapa)]-. The kinetic inertness of this novel chelate is superior by 2-3 orders of magnitude compared to non-macrocyclic MRI contrast agents approved for clinical use.

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

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Postsynthesis Modification of a Metallosalen-Containing Metal-Organic Framework for Selective Th(IV)/Ln(III) Separation

An uncoordinated salen-containing metal-organic framework (MOF) obtained through postsynthesis removal of Mn(III) ions from a metallosalen-containing MOF material has been used for selective separation of Th(IV) ion from Ln(III) ions in methanol solutions for the first time. This material exhibited an adsorption capacity of 46.345 mg of Th/g. The separation factors (beta) of Th(IV)/La(III), Th(IV)/Eu(III), and Th(IV)/Lu(III) were 10.7, 16.4, and 10.3, respectively.

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