An elegant protocol for the synthesis of N-substituted pyrroles through C–N cross coupling/aromatization process using CuFe2O4 nanoparticles as catalyst under ligand-free conditions

A simple and efficient, ligand-free C–N cross-coupling of aryl halides/benzyl bromides with trans-4-hydroxy-l-proline has been developed to produce aromatized N-substituted pyrroles, using a catalytic amount of magnetically separable and recyclable CuFe₂O₄ nanoparticles, in the presence of Cs₂CO₃ in DMSO at 100 °C.     

Synthesis of 6‐Fluoro‐7‐cyclic Amino‐substituted Dicarboxylic Acid Quinolones and their Antibacterial Activity

Novel 1‐carboxymethyl‐6‐fluoro‐7‐cyclic amino‐substituted‐4‐oxo‐1,4‐dihydroquinolone‐3‐carboxylic acids 7a , 7b , 7c , 7d , 7e , 7f , 7g , 7h , 7i , 7j , 7k , 7l , 7m , 7n were synthesized as a new class of quinolones. Ethyl‐6‐fluoro‐7‐chloro‐1,4‐dihydro‐4‐quinoline‐3‐carboxylic acid was prepared from conventional method and reacted with ethyl bromoacetate to furnish N‐carboxymethyl derivatives. The compounds were screed against various Gram‐positive and Gram‐negative bacterial strains. Antibacterial activity data is validated by molecular docking studies.     

Synthesis of N-substituted-2-aminobenzothiazoles using nano copper oxide as a recyclable catalyst under ligand-free conditions in reusable PEG-400 medium

A simple and practical method for the synthesis of N-substituted-2-aminobenzothiazoles via a crosscoupling reaction of 2-iodo anilines with isothiocyanates is envisaged using nano copper oxide as a recyclable catalyst and Cs2CO3as a base in PEG-400,as a bio-degradable,reusable,inexpensive and nontoxic reaction medium,under ligand-free conditions.The present tandem process underlines environmental acceptability to access a wide range of N-substituted-2-aminobenzothiazoles in good to excellent yields.     

Theoretical insight of nitric oxide adsorption on neutral and charged Pdn (n = 1–5) clusters

Density functional theory (DFT) calculations within the framework of generalized gradient approximation have been used to systematically investigate the adsorption of nitric oxide (NO) molecule on neutral, cationic, and anionic Pd_n (n = 1–5) clusters. NO coordinate to one Pd atom of the cluster by the end‐on mode, where the tilted end‐on structure is more favorable due to the additional electron in the π* orbital. On the contrary, in the neutral and cationic Pd₂ system, NO coordinates to the bridge site of cluster preferably by the side‐on mode. Charge transfer between Pd clusters and NO molecule and the corresponding weakening of N? O bond is an essential factor for the adsorption. The N? O stretching frequency follow the order of cationic > neutral > anionic. Binding energy of NO on anionic clusters is found to be greater than those of neutral and cationic clusters. © 2015 Wiley Periodicals, Inc.     

The Role of Methoxy Group in the Nazarov Cyclization of 1,5-bis-(2-Methoxyphenyl)-1,4-Pentadien-3-one in the Gas Phase and Condensed Phase

ESI-protonated 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one (1) undergoes a gas-phase Nazarov cyclization and dissociates via expulsions of ketene and anisole. The dissociations of the [M + D]⁺ ions are accompanied by limited HD scrambling that supports the proposed cyclization. Solution cyclization of 1 was effected to yield the cyclic ketone, 2,3-bis-(2-methoxyphenyl)-cyclopent-2-ene-1-one, (2) on a time scale that is significantly shorter than the time for cyclization of dibenzalacetone. The dissociation characteristics of the ESI-generated [M + H]⁺ ion of the synthetic cyclic ketone closely resemble those of 1, suggesting that gas-phase and solution cyclization products are the same. Additional mechanistic studies by density functional theory (DFT) methods of the gas-phase reaction reveals that the initial cyclization is followed by two sequential 1,2-aryl migrations that account for the observed structure of the cyclic product in the gas phase and solution. Furthermore, the DFT calculations show that the methoxy group serves as a catalyst for the proton migrations necessary for both cyclization and fragmentation after aryl migration. An isomer formed by moving the 2-methoxy to the 4-position requires relatively higher collision energy for the elimination of anisole, as is consistent with DFT calculations. Replacement of the 2-methoxy group with an OH shows that the cyclization followed by aryl migration and elimination of phenol occurs from the [M + H]⁺ ion at low energy similar to that for 1.

Selective Halogenation Using an Aniline Catalyst

Electrophilic halogenation is used to produce a wide variety of halogenated compounds. Previously reported methods have been developed mainly using a reagent‐based approach. Unfortunately, a suitable “catalytic” process for halogen transfer reactions has yet to be achieved. In this study, arylamines have been found to generate an N‐halo arylamine intermediate, which acts as a highly reactive but selective catalytic electrophilic halogen source. A wide variety of heteroaromatic and aromatic compounds are halogenated using commercially available N‐halosuccinimides, for example, NCS, NBS, and NIS, with good to excellent yields and with very high selectivity. In the case of unactivated double bonds, allylic chlorides are obtained under chlorination conditions, whereas bromocyclization occurs for polyolefin. The reactivity of the catalyst can be tuned by varying the electronic properties of the arene moiety of catalyst.     

Sensitive method for the determination of paricalcitol by liquid chromatography and mass spectrometry and its application to a clinical pharmacokinetic study

A highly sensitive, specific and rapid LC‐ESI‐MS/MS method has been developed and validated for the quantification of paricalcitol (PAR) in human plasma (500 μL) using paricalcitol‐d₆ (PAR‐d₆) as an internal standard (IS) as per regulatory guidelines. A liquid–liquid extraction method was used to extract the analyte and IS from human plasma. Chromatography was achieved on Zorbax SB C₁₈ column using an isocratic mobile phase in a gradient flow. The total chromatographic run time was 6.0 min and the elution of PAR and PAR‐d₆ occurred at ~2.6 min. A linear response function was established for the range of concentrations 10–500 pg/mL in human plasma. The intra‐ and inter‐day accuracy and precision values for PAR met the acceptance criteria. The validated assay was applied to quantitate PAR concentrations in human plasma following oral administration of 4 µg capsules to humans. Copyright © 2014 John Wiley & Sons, Ltd.