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A 3D Homochiral MOF [Cd2(d-cam)3]?2Hdma?4dma for HPLC Chromatographic Enantioseparation

Up to now, some chiral metal-organic frameworks (MOFs) have been reported for enantioseparation in liquid chromatography. Here we report a homochiral MOF, [Cd2(d-cam)3]·2Hdma·4dma, used as a new chiral stationary phase for high-performance liquid chromatographic enantioseparation. Nine racemates of alcohol, naphthol, ketone, and base compounds were used as analytes for evaluating the separation properties of the chiral MOF packed column. Moreover, some effects such as mobile phase composition, column temperature, and analytes mass for separations on this chiral column also were investigated. The relative standard deviations for the resolution values of run-to-run and column-to-column were less than 2.1% and 3.2%, respectively. The experimental results indicate that the homochiral MOF offered good recognition ability, which promotes the application of chiral MOFs use as stationary phase for enantioseparation. Chirality 28:340-346, 2016.

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

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Oxidative coupling of 2-naphthol to (R)/(S)-BINOL by MCM-41 supported Mn-chiral Schiff base complexes

Three Mn(III)-chiral Schiff base complexes supported on MCM-41 are found to be effective reusable catalysts for enantioselective oxidation of 2-naphthol to (R)- and (S)-BINOL (1,1? bi-2-naphthol) in the presence of oxygen. The supported Mn(III)-complexes are characterized by PXRD, FTIR, solid state-NMR, BET, and cyclic voltammetry study. The homo-coupling reaction with oxygen as the oxidant is promoted by 20 mg of Mn(III) Schiff base complexes to afford binaphthols in nearly quantitative yields with high enantioselectivity of up to 91% ee. The catalytic activities of the homogeneous and heterogeneous chiral catalyst are found to be almost similar. However, the heterogeneous counterparts are found to be advantageous in terms of recyclability and storability. Oxygen partial pressure, the nature of the solvent, temperature and the amount of catalyst affect the catalytic oxidation process. High temperature and highly polar solvent are found to have adverse effects on the catalytic oxidation process.

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

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Tunable phosphinite, phosphite and phosphoramidite ligands for the asymmetric hydrovinylation reactions

Only a limited number of ligands have been successfully employed for the Ni-catalyzed asymmetric hydrovinylation reaction. Diarylphosphinites, carrying beta-acylamino groups prepared from readily available carbohydrates, in conjunction with highly dissociated counteranions {[(3,5-(CF3) 2C6H3]4B- or SbF 6-}, effect the hydrovinylation of vinylarenes under ambient pressure of ethylene with high enantioselectivity. Nitrogen substituents such as -COCF3 and COPh groups lead to isomerization of the primary products (3-arylbutenes) to Z- and E-2-aryl-2-butenes. In a prototypical synthesis of a 2-arylproionic acid, (S)-3-(4-bromophenyl)-1-butene (89% ee) has be transformed into (R)-ibuprofen by Ni-catalyzed cross-coupling with i-BuMgBr, followed by oxidation of the double bond with NaIO4 and KMnO 4. Asymmetric codimerization of norbonene and ethylene using binaphthol-derived phosphoramidites as ligands gives 1:1, 2:1 or polymeric adducts depending on the relative configurations and nature of the BINAP and amine moieties. With one of the phosphoramidite-Ni complexes, counteranions BAr4- [Ar=3,5-(CF3)2C 6H3] and SbF6-, which had been used interchangeably in other reactions, give either a 1:1 adduct or a 2:1 adduct, respectively.

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

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Preparation of Optically Active 2,2′-Dihydroxy-1,1′-binaphthyl via Microbial Resolution of the Corresponding Racemic Diester

An efficient microbial resolution of 2,2′-dihydroxy-1,1′-binaphthyl has been achieved by exposing the corresponding dibutyrate to Bacillus sp; the importance of the size of the ester group for the hydrolysis rate and selectivity is emphasized.

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

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The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 18531-94-7 is helpful to your research. Computed Properties of C20H14O2

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New Helical Molecules, X. Syntheses and Chiroptical Properties of Diastereomeric and Enantiomeric Pure Thiophenophanes

The functionalized helical-chiral compounds 2-4 and 6, 7 are synthesized.The diastereomers 4a, b and 7a, b are separated.The X-ray analysis proves the P-(+) configuration for 7a and a high torsion angle of 19.8 deg between the rings A , B and C (Figure 1).The Hi protons of the two m-phenylene moieties of 2-4 and 6, 7 show different chemical shifts of about 0.5 ppm.From a correlation of the CD curves of 4 and 6, 7 and the X-ray structure of 7a the absolute configuration of derivatives of 1 can be elucidated.

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

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BISAMINOIMINE LIGAND AND CATALYST HAVING BINAPHTHOL SKELETON

PROBLEM TO BE SOLVED: To provide a ligand for supplying a reaction field that is rich in flexibility and is flexible in response to individual reactions and a catalyst using the same. SOLUTION: This invention relates to a ligand represented by formula (1), where R1-R4 are hydrogen or a substituent. COPYRIGHT: (C)2015,JPO&INPIT

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

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THE X-RAY CRYSTAL STRUCTURE AND PACKING MODE OF (+/-)-2-THIONO-2-MERCAPTO-alpha,alpha’-DINAPHTHO-(d,f)(1,3,2)-DIOXOPHOSPHEPIN – A CLATHRATE STRUCTURE

(+/-)-2-Thiono-2-mercapto-alpha,alpha’-dinaphtho-(d,f)(1,3,2)-dioxophosphepin and a number of related compounds which contain a cyclic phosphoric ring all manifested clathrating properties.An X-ray examination of the p-xylene clathrate revealed that the main mode of action in this new class of clathrates is exclusively derived from the topological interaction of the host molecules, the alternating chirality of the binaphthyl unit plays a decisive role in the cavity making.

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

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Rational design of homochiral solids based on two-dimensional metal carboxylates

A chiral two-dimensional network is the basis for the structure of a homochiral solid exploiting metal-carboxylate coordination. The synthesis involved enantiopure bridging ligands and metal-organic secondary building units (SBUs), and resulted in ethoxy-protected BINOL functionalities pointing into the cavities in this crystalline chiral zeolitic material (see picture).

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

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Readily accessible, modular, and tuneable BINOL 3,3?- perfluoroalkylsulfones: Highly efficient catalysts for enantioselective in-mediated imine allylation

Thia-Fries rearrangement of BINOL perfluoroalkylsulfonates affords readily derivatized novel mono- and disulfone ligands in just two steps from enantiomerically pure BINOL. These electron-demanding BINOLs have been successfully applied as catalysts for indium-mediated allylation of N-acylhydrazones. A general and highly enantioselective catalytic process is described, in which the presence of two perfluoroalkylsulfone (SO2RF) groups is shown to be crucial for activity and selectivity. The allylation process affords the corresponding homoallylic amines up to 99% yield and 99% ee. Copyright

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

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1,1?-Binaphthyl-2,2?-diyl phosphoroselenoyl chloride as a chiral molecular tool for the preparation of enantiomerically pure alcohols and amines

Enantiomerically pure phosphoroselenoyl chloride bearing a binaphthyl group was synthesized. This phosphoroselenoyl chloride was used to discriminate and resolve simple secondary alcohols. Stereospecific conversions of diastereomerically pure phosphoroselenoic acid esters, obtained by reaction of the chloride with simple secondary alcohols, to enantiomerically pure alcohols and amines were also achieved. Copyright

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