Category: 20439-47-8

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Stable anilinyl radicals coordinated to nickel: X-ray crystal structure and characterization

Two anilinosalen and a mixed phenol-anilinosalen ligands involving sterically hindered anilines moieties were synthesized. Their nickel(II) complexes 1, 2, and 3 were prepared and characterized. They could be readily one-electron oxidized (E1/2=-0.30, -0.26 and 0.10 V vs. Fc +/Fc, respectively) into anilinyl radicals species [1]+, [2]+, and [3]+, respectively. The radical complexes are extremely stable and were isolated as single crystals. X-ray crystallographic structures reveal that the changes in bond length resulting from oxidation do not exceed 0.02 A within the ligand framework in the symmetrical [1] + and [2]+. No quinoid bond pattern was present. In contrast, larger structural rearrangements were evidenced for the unsymmetrical [3]+, with shortening of one Cortho-Cmeta bond. Radical species [1]+ and [2]+ exhibit a strong absorption band at around 6000 cm-1 (class III mixed valence compounds). This band is significantly less intense than [3]+, consistent with a rather localized anilinyl radical character, and thus a classification of this species as class II mixed-valence compound. Magnetic and electronic properties, as well as structural parameters, have been computed by DFT methods.

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

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Enantioselective Recognition for Many Different Kinds of Chiral Guests by One Chiral Receptor Based on Tetraphenylethylene Cyclohexylbisurea

A neutral chiral receptor based on TPE cyclohexylbisurea was synthesized and could discriminate the enantiomers of many different kinds of chiral reagents, including chiral acidic compounds, basic compounds, amino acids, and even neutral alcohols. The 1H NMR spectra disclosed that the ability of chiral recognition could be ascribed to the multiple hydrogen bonds and CH interactions between the TPE urea receptor and the enantiomer of the chiral guest, which led to the selective aggregation of the receptor with one of the two enantiomers. This result exhibited a great potential in enantiomer discernment and high-throughput analysis of enantiomer composition of these chiral analytes by one chiral AIE molecule.

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

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Cytotoxic titanium(IV) complexes of chiral diaminobis(phenolato) ligands: Better combination of activity and stability by the bipyrrolidine moiety

Racemic and enantiomerically pure titanium(IV) complexes with ortho-bromo-para-methyl-substituted diaminobis(phenolato) ligands were prepared with NH-, NMe-, and bipyrrolidine-based diamino bridges through ligand-to-metal chiral induction. The hydrolytic stability of the complexes was evaluated, and their cytotoxicity was measured using HT-29 human colon cancer cells based on the MTT assay. All stereochemical forms of the NMe-based complexes, although demonstrating the highest hydrolytic stability, were biologically inactive. For the NH and bipyrrolidine-based active complexes, the pure enantiomers exhibited high cytotoxicity whereas the racemic mixtures were inactive, supporting the involvement of a polynuclear active species. The bipyrrolidine complexes appear to provide the best combination of hydrolytic stability and biological activity, presumably by minimizing steric bulk and consequently enabling biological accessibility. Racemic and optically pure phenolato titanium(IV) complexes were prepared with NH, NMe, and bipyrrolidine-based diamino bridges. The optically pure bipyrrolidine complexes provide the best combination of hydrolytic stability and biological activity, presumably by maintaining small enough steric bulk to enable biological accessibility. Copyright

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

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New chiral Schiff base-zinc complexes and their esterolytic catalytic activity

A new series of chiral Zn-Schiff base (imine) complexes has been prepared from mono-N-sulfonyl derivatives of (1R,2R)-diaminocyclohexane, N-heterocyclic aldehydes, and zinc salts. The formation and characterization of the (L)ZnX 2 complexes was established by NMR, IR and HRESI-MS. Spectroscopic and kinetic evidence indicates that these ligands may be bidentate or tridentate depending on conditions of the medium. The methanolysis of a chiral, racemic picolinate ester catalyzed by the Zn(II)-Schiff base complexes was studied kinetically. The rate constants were found to vary approximately a hundred-fold and in a complex way depending on the imine ligand and the Zn-counter anion, kobs = 5.0 ¡Á 10-6-4.8 ¡Á 10-4 M -1 s-1. A Job plot analysis of ternary complex formation of LZnX2 with two phosphonate transition state analogs suggests that two types of (imine)Zn(picolinate)X ternary complexes may be intermediates and that varying rate-limiting steps may be involved in the LZnX2- catalyzed methanolysis of picolinate esters.

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

Chemistry is traditionally divided into organic and inorganic chemistry. Product Details of 20439-47-8. The former is the study of compounds containing at least one carbon-hydrogen bonds.In a patent£¬Which mentioned a new discovery about 20439-47-8

Stereoselective Protonation of Carbanions, 4. Enantioselective Protonation of Lactone Enolates

The prochiral lithium enolates derived from the five-membered lactones rac-1 and rac-2 were protonated by 37 OH- and 21 NH-chiral proton sources in THF at -78 deg C.The enantioselectivities, determined directly from the reaction mixture by chiral HPLC, are always higher for system 1, probably due to restricted rotation of the phenyl group in 1Li at low temperature (NMR) and range from 0-54percent ee.The strongest stereodifferentiation is observed if the OH or NH acids carry an adjacent O- or N-containing group (structures G-J0 which allows complexation with the lithium ion.A plausible transition state involving the dimeric lithium enolate is proposed. – Key Words: Protonation / Enantioselectivity / Lactone enolates / Chiral proton sources

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

Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 20439-47-8, molcular formula is C6H14N2, introducing its new discovery. name: (1R,2R)-Cyclohexane-1,2-diamine

Asymmetric organocatalytic efficiency of synthesized chiral beta-amino alcohols in ring-opening of glycidol with phenols

A series of novel chiral beta-amino alcohols 3-5 and 7-10 were synthesized by regioselective ring opening of epoxides and chiral amines with a straightforward method in high yields (up to 99 %). Kinetic resolution of racemic glycidol with phenols was achieved by using chiral amino alcohols as organocatalysts. Amino alcohols 5, 8 and 10 exhibited the highest enantioselectivities with p-cresol, phenol, and p-methoxyphenol by 63, 65, 58 % ee, respectively. The moderate enantioselectivities were observed with catalyst 9b towards all the nucleophiles (34-48 % ee). The ee values of the desired 3-aryloxy-1, 2-diols were determined by HPLC. This study presents an attractive tool for the synthesis of beta-blockers and structurally complex molecules.

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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, Recommanded Product: (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 Alfonso, Ignacio£¬once mentioned of 20439-47-8

Sequential biocatalytic resolution of (¡À)-trans-cyclohexane-1,2-diamine. Chemoenzymatic synthesis of an optically active polyamine

Candida antarctica lipase-catalysed double monoaminolysis of dimethyl malonate by (¡À)-trans-cyclohexane-1,2-diamine allows the sequential resolution of the latter compound, affording an enantiopure bis(amidoester), (R,R)-3, which is subsequently transformed into an optically active polyamine, (R,R)-9.

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

Electric Literature of 20439-47-8, In heterogeneous catalysis, the catalyst is in a different phase from the reactants. At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 20439-47-8, name is (1R,2R)-Cyclohexane-1,2-diamine. In an article£¬Which mentioned a new discovery about 20439-47-8

COMPOUNDS, COMPOSITIONS AND METHODS FOR THE TREATMENT OF AMYLOID DISEASES AND SYNUCLEINOPATHIES SUCH AS ALZHEIMER’S DISEASE, TYPE 2 DIABETES, AND PARKINSON’S DISEASE

Bis- and tris-dihydroxyaryl compounds and their methylenedioxy analogs and pharmaceutically acceptable esters, their synthesis, pharmaceutical compositions containing them, and their use in the treatment of amyloid diseases, especially Ass amyloidosis, such as observed in Alzheimer’s disease, IAPP amyloidosis, such as observed in type 2 diabetes, and synucleinophathies, such as observed in Parkinson’s disease, and the manufacture of medicaments for such treatment.

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

Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 20439-47-8, molcular formula is C6H14N2, introducing its new discovery. name: (1R,2R)-Cyclohexane-1,2-diamine

Total synthesis of (-)-virginiamycin m2: Application of crotylsilanes accessed by enantioselective Rh(II) or Cu(I) promoted carbenoid Si-H insertion

A stereoselective synthesis of the antibiotic (-)-virginiamycin M 2 is detailed. A convergent strategy was utilized that proceeded in 10 steps (longest linear sequence) from enantioenriched silane (S)-15. This reagent, which was prepared via a Rh(II)- or Cu(I)-catalyzed carbenoid Si-H insertion, was used to introduce the desired olefin geometry and stereocenters of the C1-C5 propionate subunit. A modified Negishi cross-coupling or an efficient alkoxide-directed titanium-mediated alkyne-alkyne reductive coupling strategy was utilized to assemble the trisubstituted (E,-E)-diene. An underutilized late-stage SmI2-mediated macrocyclization was employed to construct the 23-membered macrocycle scaffold of the natural product (Figure presented).

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

Chemistry is an experimental science, Quality Control of: (1R,2R)-Cyclohexane-1,2-diamine, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 20439-47-8, Name is (1R,2R)-Cyclohexane-1,2-diamine

Diamidophosphite based on (1R,2R)-1,2-bis(3-hydroxybenzamido)cyclohexane in Pd-catalyzed enantioselective allylation

Diamidophosphite ligand bearing (1R,2R)-1,2-bis(3-hydroxybenzamido)cyclohexane fragment and stereogenic phosphorus atoms in the 1,3,2-diazaphopholidine cycles was synthesized. Catalytic performance of this ligand was evaluated in asymmetric allylic substitution. In the reactions involving (E)-1,3-diphenyl allyl acetate as a substrate, up to 94% ee in alkylation with dimethyl malonate and up to 68% ee in amination with pyrrolidine was achieved in the presence of this ligand.

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