One-pot synthesis of 1, 2-dihydro [1,2,4] triazinium salt by copperassisted unprecedented cyclization reaction: Application in protein binding.

Copper catalyzed intramolecular annulation of 2-((2benzylidene-1-phenylhydrazineyl)methyl)pyridine derivatives was described. It was found that Cu(II) is reduced under the reaction condition to Cu(I). Synthesized 1, 2-dihydro [1,2,4] triazinium salt showed fluorescence activity in solid state. On treating with base, an instant increase in fluorescence was observed. A detailed physicochemical assessment underscored the robust DNA-binding prowess of the [1,2,4] triazinium cationic species (C1-C3) via intercalative mechanisms. Notably, binding assays with BSA accentuated the heightened nucleic acid affinity of these cationic species.

Methyl Formate, an Alternative Transfer Hydrogenating Agent for Chemoselective Reduction of N-Heteroarenes and Azoarenes.

The search for efficient molecular hydrogen precursors and their catalytic exploration is necessary for the evolution of catalytic transfer hydrogenation. Methyl formate (MF) having high hydrogen content still remains unexplored for such transformations. Herein, we disclosed a bifunctional Ir(III)-complex catalyzed chemoselective TH protocol for N-heteroarenes and azoarenes using MF. A variety of substrates including ten bioactive molecules have been synthesized under mild reaction conditions. A probable mechanistic pathway was proposed based on control experiments and mechanistic studies.

Crystal structure of a phenoxyl radical complex relevant to the metal site of the galactose oxidase enzyme: A facile one-pot synthesis, evidence for hydrogen atom transfer and DNA cleavage via self-activation.

Copper complexes [Cu(L1H)ClO4] (1) and [Cu(L2)NO3] (2), which are relevant to the metal site of the galactose oxidase enzyme, were synthesized and characterized by different spectroscopic methods. L1H2 and L2H2 [where L1H2 stands for 2,2'-((1E,1'E)(2,2'-(pyridine-2,6-diyl)bis(2-phenylhydrazin-2-yl-1-ylidene))bis(methanylylidene))diphenol and L2H2 stands for 6,6'-((1E,1'E)-(2,2'-(pyridine-2,6-diyl)bis(2-phenylhydrazin-2-yl-1-ylidene))bis(methanylylidene))bis(2,4-di-tert-butylphenol), H stands for dissociable proton] are pentadentate ligands. These ligands provide pyridyl N, two imine N, and two non-innocent phenoxyl and phenolato O donors, forming complex 1 as a non-radical complex, while complex 2 is a phenoxyl radical complex. The molecular structures of complexes 1 and 2 were authenticated by X-ray crystallography. Benzyl alcohol oxidation was investigated, and the conversion of 9,10-dihydroanthracene to anthracene was examined to scrutinize the H-atom abstraction reaction. Nuclease activity with complexes 1 and 2 was investigated by self-activated plasmid DNA (pBR322) cleavage. Non-innocent properties of the ligand-containing phenolato function were investigated by DFT calculations.

Design and synthesis of novel palladium cyclometallate-based fluorescent probe: Studies on interaction with cell membrane by confocal and fluorescence lifetime imaging.

Coordination complexes offer great potential as cellular imaging probes, which allow to examine specific cell organelle structures in their physiological conditions to better understand the biological system. Understanding the heterogeneous nature of the cell membrane could unveil details of their functionality. Here, we have developed a new anthracene conjugated fluorescent palladium(II) cyclometallate [PdL1Cl] where L1H = [2-(2- (anthracen-9-ylmethylene)-1-phenylhydrazineyl)pyridine] (H stands for dissociable proton), which not only specifically stains the cell membrane, but could be utilized to visualise the membrane by the confocal and fluorescence lifetime imaging microscopy (FLIM). This probe is unable to enter inside the cell as it did not pass through the cell membrane via diffusion or various organic and metal transporters. However, the great lipophilicity of fluorescein improves the interaction of the probe with the peptidoglycan layer of the cell membrane. Probable dissociation of chloride ion and formation of positively charged palladium complex resulted in staining the negatively charged cell membrane. The 3D confocal imaging clearly expressed sole membrane staining by the probe. The probe efficiently stains both cancer cells (HeLa and MCF-7 cell lines) and normal cell (HEK 293 T), confirming the universality of the probe in membrane staining.

Well-Defined Phosphine-Free Manganese(II)-Complex-Catalyzed Synthesis of Quinolines, Pyrroles, and Pyridines.

Herein, we report a simple, phosphine-free, and inexpensive catalytic system based on a manganese(II) complex for synthesizing different important N-heterocycles such as quinolines, pyrroles, and pyridines from amino alcohols and ketones. Several control experiments, kinetic studies, and DFT calculations were carried out to support the plausible reaction mechanism. We also detected two potential intermediates in the catalytic cycle using ESI-MS analysis. Based on these studies, a metal-ligand cooperative mechanism was proposed.

Designed pincer ligand supported Co(II)-based catalysts for dehydrogenative activation of alcohols: Studies on N-alkylation of amines, α-alkylation of ketones and synthesis of quinolines.

Base-metal catalysts Co1, Co2 and Co3 were synthesized from designed pincer ligands L1, L2 and L3 having NNN donor atoms respectively. Co1, Co2 and Co3 were characterized by IR, UV-Vis. and ESI-MS spectroscopic studies. Single crystal X-ray diffraction studies were investigated to authenticate the molecular structures of Co1 and Co3. Catalysts Co1, Co2 and Co3 were utilized to study the dehydrogenative activation of alcohols for N-alkylation of amines, α-alkylation of ketones and synthesis of quinolines. Under optimized reaction conditions, a broad range of substrates including alcohols, anilines and ketones were exploited. A series of control experiments for N-alkylation of amines, α-alkylation of ketones and synthesis of quinolines were examined to understand the reaction pathway. ESI-MS spectral studies were investigated to characterize cobalt-alkoxide and cobalt-hydride intermediates. Reduction of styrene by evolved hydrogen gas during the reaction was investigated to authenticate the dehydrogenative nature of the catalysts. Probable reaction pathways were proposed for N-alkylation of amines, α-alkylation of ketones and synthesis of quinolines on the basis of control experiments and detection of reaction intermediates.

Ferrocenyl palladacycles derived from unsymmetrical pincer-type ligands: evidence of Pd(0) nanoparticle generation during the Suzuki-Miyaura reaction and applications in the direct arylation of thiazoles and isoxazoles.

A new family of ferrocenyl-palladacycle complexes Pd(L1)Cl (Pd1) and Pd(L2)Cl (Pd2) were synthesized and characterized by UV-visible, IR, ESI-MS, and NMR spectral studies. The molecular structures of Pd1 and Pd2 were determined by X-ray crystallographic studies. Palladacycle catalyzed Suzuki-Miyaura cross-coupling reactions were investigated utilizing the derivatives of phenylboronic acids and substituted chlorobenzenes. Mechanistic investigation authenticated the generation of Pd(0) nanoparticles during the catalytic cycle and the nanoparticles were characterized by XPS, SEM and TEM analysis. Direct C-H arylation of thiazole and isoxazole derivatives employing these ferrocenyl-palladacycle complexes was examined. The reaction model for the arylation reaction implicating the in situ generation of Pd(0) nanoparticles was proposed.