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Formation, electrochemical and radical scavenging properties of novel ruthenium compounds with N, X-donor (X = O, N) heterocyclic chelators

Herein, we communicate the formation of novel ruthenium compounds with N, X-donor (X = O, N) heterocyclic-derived ligands. A paramagnetic ruthenium(IV) complex, [RuCl(pho)(bzca)(PPh3)](1) (pho = 2-aminophenolate; bzca = 2-carboxylate-1H-benzimidazole) was isolated from the reaction of the ruthenium(II) precursor, trans-[RuCl2(PPh3)3] and 2-((1H-benzimidazole)methylamino)phenol (Hbzap). The 1:1 molar reaction between the same metal precursor and N-(benzoxazole)-2-hydroxybenzamide (H2bhb) led to the formation of cis-Cl, trans-P-[RuIII(Hbhb)Cl2(PPh3)2](2). The dinuclear ruthenium compounds, (mu-Htba,Cl)2[RuIICl(PPh3)]2(3) (Htba = N-(thiophene)methyl-benzoxazole-2-amine) and (mu-Cl)2[RuIIICl(Hchpr)(PPh3)]2(4) (H2chpr = 2-amino-3-((tetrahydro-2H-pyran-4-ylimino)methyl)-4H-chromen-4-one) were formed from the equimolar ratio coordination reactions between trans-[RuCl2(PPh3)3] and the respective free-ligands, Htba and H2chpr. These metal complexes were characterized via IR-, NMR- and UV-Vis spectroscopy, molar conductivity measurements and structural elucidations were confirmed by single crystal X-ray analysis. The X-ray studies revealed that all the metallic compounds exhibited octahedral geometries and that the Hbzap free ligand has undergone a unique molecular transformation to afford the pho and bzca bidentate chelators in 1. The electrochemical properties of the respective metal complexes were investigated by voltammetric analysis. The cyclic voltammograms (CVs) of 1-3 showed one redox couple while within the CV of the dinuclear compound 4, two redox couples were observed. The ligands and their metal complexes were also subjected to DPPH radical scavenging studies. The IC50 values showed that all the metallic compounds have higher radical scavenging activities than their corresponding free-ligands and the natural antioxidant, Vitamin C.

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Synthesis, anticancer and antioxidant activities of some novel N-(benzo[d]oxazol-2-yl)-2-(7- or 5-substituted-2-oxoindolin-3-ylidene) hydrazinecarboxamide derivatives

A series of N-(benzo[d]oxazol-2-yl)-2-(7- or 5-substituted-2-oxoindolin-3- ylidene) hydrazinecarboxamide derivatives were synthesized by treating N-(benzoxazol-2-yl)hydrazinecarboxamide with different isatin derivatives. The newly synthesized compounds were characterized on the basis of spectral analyses. All the synthesized derivatives (Va-l) were screened for anticancer and antioxidant activities. The results showed the anticancer activity of test compounds against HeLa, IMR-32 and MCF-7 cancer cell lines using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. All the synthetic compounds produced a dose-dependant inhibition of growth of the cells. The IC50 values of some compounds were comparable with standard anticancer agent, cisplatin. All the title compounds effectively scavenged the free radical, alpha,alpha-diphenyl-beta-picryl hydrazyl. The test compounds having substitution with different halides (electron withdrawing groups) at C5 position showed more potent anticancer and antioxidant activities than those at C7 position. These results indicate that C5-substituted derivatives may be useful for developing antioxidant agents that play a protective role in many pathological conditions such as cancer, diabetes and so on.

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NiCl2-catalyzed cascade reaction of isocyanides with functionalized anilines

A NiCl2-catalyzed isocyanide insertion reaction of anilines bearing another nucleophile functional group utilizing TEMPO as oxidant in isopropyl ethanoate (IPA) or THF has been reported. This simple and general method could afford 2-aminobenzimidazole, 2-aminobenzothiazole, 2-aminobenzoxazole, as well as 2-aminobenzo[d][1,3]oxazine in moderate to excellent yields (up to 95% yield).

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Formation of nitrogen-containing heterocycles using di(imidazole-1-yl)methanimine

A mild and efficient synthesis of five- and six-membered nitrogen containing heterocyclic compounds, in which di(imidazole-1-yl)methanimine serves as a one-carbon source, is reported.

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REACTION OF 2-AMINOBENZOXAZOLES WITH COMPOUNDS WITH ACTIVATED MULTIPLE BONDS

The reaction of 2-aminobenzoxazoles with activated alkenes of the acrylic acid type and its derivatives and methyl vinyl ketone proceeds in the presence of basic catalysts to give products of mono- and diaddition at the exocyclic nitrogen atom.The reaction of 5(6)-substituted 2-aminobenzoxazoles with esters of propyl and acetylenedicarboxylic acids in the absence of catalysts leads to the production of condensed 2-oxopyrimidines.The effect of substituents and the reaction conditions on the course of the process was investigated.

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Development and scale-up of an efficient miyaura borylation process using tetrahydroxydiboron

A revised Miyaura borylation process has been developed using tetrahydroxydiboron that avoids the use of bis(pinacolato) diboron and hence the need to hydrolyze the resulting boronic ester to its corresponding acid. The process was greatly simplified and successfully scaled-up in the pilot plant on a 65 kg scale, reducing plant cycle time and resulting in a 47% overall cost reduction. Furthermore, methodology for the study of the oxygen sensitivity of the process is reported that allowed for optimization of the amount of tetrahydroxydiboron and catalyst used. These studies also demonstrated an oxygen-induced decomposition of tetrahydroxydiboron.

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Development of electroorganic reactions utilizing stabilized reactive species and its application to organic energy storage materials

Reactive species generated by the oxidation and reduction of organic compounds are generally unstable. To utilize the reactive species as intermediates for organic synthesis and functional materials, it is crucial how to treat them. In this headline, electrochemical reactions utilizing stabilized reactive cations, which enabled benzylic C-H/aromatic C-H cross-coupling, aromatic C-H/C-H cross-coupling, and aromatic C-H amination are demonstrated. Furthermore, energy storage materials utilizing stabilized anions, which enabled to develop organic materials for lithium-ion batteries with high voltage of ca. 3V and solvent-free redox flow batteries with high energy density, are demonstrated. These studies show the usefulness of stabilized reactive species.

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Synthesis and Antibacterial Activity of Benzazolyl Azolyl Sulfamoyl Acetamides

A new class of benzazolyl azolyl sulfamoyl acetamides was prepared from azolyl sulfamoyl acetates and benzazolyl amines in the presence of KOtBu in tetrahydrofuran. Compounds with benzothiazole-thiazole, benzimidazole-thiazole, benzothiazole-imidazole, and benzimidazole-imidazole moieties exhibited excellent antibacterial activity against Bacillus subtilis.

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2-Benzamido-N-(1H-benzo[d]imidazol-2-yl)thiazole-4-carboxamide derivatives as potent inhibitors of CK1delta/epsilon

In this study we identified two heterocyclic compounds (5 and 6) as potent and specific inhibitors of CK1delta (IC50 = 0.040 and 0.042 muM, respectively). Whereas compound 5 exhibited fivefold higher affinity towards CK1delta than to CK1epsilon (IC50 CK1epsilon = 0.199 muM), compound 6 also inhibited CK1epsilon (IC50 = 0.0326 muM) in the same range as CK1delta. Selected compound 5 was screened over 442 kinases identifying 5 as Ahighly potent and selective inhibitor of CK1delta. X-ray analysis of 5 bound to CK1delta demonstrated its binding mode. In addition, characterization of 5 and 6 in Acell biological approach revealed the ability of both compounds to inhibit proliferation of tumor cell lines in Adose and cell line specific manner. In summary, our optimizations lead to the development of new highly selective CK1delta and epsilon specific inhibitors with biological activity.

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2-Aminobenzimidazole and -benzoxazole as N-nucleophile in palladium-catalysed aminocarbonylation

Palladium-catalysed aminocarbonylation of aryl iodides in the presence of 2-aminobenzimidazole and 2-aminobenzoxazole as N-nucleophile was carried out. Single CO insertion took place, however, instead of the expected carboxamides (C(O)NH) the corresponding N-acyl-imine (C(O)N[dbnd]C) derivatives were obtained. The structure of the latter compounds can be explained by tautomerization involving the heterocyclic ring. The above structures without amide-NH moieties were proved by methylation at the NH groups of the heterocycle. The resulted mono- and dimethylated benzimidazole derivatives, as well as monomethylated benzoxazole derivatives, like the parent N-acylated compounds, were fully characterised including single crystal X-ray crystallography.

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Benzoxazole – Wikipedia,
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