A series of 2,3-dihydro-1,5-benzodiazepine derivatives have been synthesized and characterized using IR, NMR, GC-MS, single crystal XRD, and microanalysis. The results of their antibacterial activity against methicillin-resistance Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Bacillus subtilis, Streptococcus mutans, Pseudomonas aeruginosa, Salmonella typhi, and Streptococcus pyrogens indicated that most of the compounds were bacteriostatic (0.125−4 mg/mL) and also exhibited good biofilm inhibition (0.21−72.69%). The compounds were found to be synergistic when used in combination with other antibiotics. The antiproliferative and cytotoxic effects were also investigated against PC-3 prostate cancer and RAW 264.7 macrophage cell lines, respectively, using the MTT assay. Apart from compounds 6 and 7, a good number of the compounds (1, 2, 3, 4, 5, and 8) were selectively toxic to the prostate cancer cells at 20 µM, whilst sparing the normal cells. Compound 3 demonstrated the highest antiprostate cancer effect by reducing the viability of PC-3 cells to (13.75%), which was followed by compounds 1 (47.72%), 2 (48.18%), 4 (62.61%), 5 (66.70%), and 8 (69.55%).

Phosphole P(V) derivatives are interesting building blocks for various applications from ligand synthesis to material sciences. We herein describe the preparation and characterisation of new 2,4-disubstituted oxo-, thiooxo-, and selenooxophospholes. The nature of the substituents on the phosphole ring determines the reactivity of these compounds towards homodimerization reactions. Aryl and trimethylsilyl substituted oxophospholes undergo selective [4+2] dimerization, whereas, for thiooxo- and selenooxophospholes, light-induced, selective [2+2] head-to-head dimerization occurs in the case of aryl substituents. DFT calculations provide some insights on these differences in reactivity.

Abstract This account summarizes representative contributions of Prof. Naomichi Furukawa to the field of heteroatom chemistry. Ligand‐coupling reactions (LCRs) and ligand‐exchange reactions (LERs) of chalcogen derivatives were developed from reactions of trivalent chalcogen species with organometallic reagents. Prof. Furukawa has also reported a large number of mono‐ and dicationic compounds generated via transannular and intermolecular interactions. Furthermore, the detection and isolation of hypercoordinated chalcogen species bearing only carbon ligands and an efficient method for the synthesis of thiophene S‐oxides and their reactivity are described.

Abstract We report the attempted synthesis of a “masked” phosphaalkene by treating MgA·3THF (A = anthracenide) with MesPCl(CH2Cl). Although the desired “masked” phosphaalkene could not be isolated, indirect evidence for its formation was obtained. The product of trapping MesP=CH2 with 1,3‐cyclohexadiene was detected. In addition, the oxide MesPO(Me)A was isolated and crystallographically characterized from the MgA·3THF and MesPCl(CH2Cl) experiment described above. Finally, the attempted isolation of “masked” phoshaalkene afforded P‐containing oligomers with a trimodal molecular weight distribution [Mn = 640, 1.7 × 103 and 7.4 × 103 Da].

Abstract The synthesis of a novel class of fluorous ionic liquids was investigated. The 2,6‐diperfluoroalkyl‐substituted pyridinium salts 2b‐f were solids at ambient temperature and insoluble in perfluoromethylcyclohexane. The addition of much further fluorous alkyl group to nitrogen atom of 2,6‐disubstituted pyridines 1 did not proceed to afford the pyridinium salts 3 having two or three perfluoroalkyl groups. On the other hand, the reaction of 3,5‐diperfluoroalkyl‐substituted pyridine 4 with perfluoroalkyl iodide proceeded to give N‐perfluoroalkylpyridinium salts 6a and 7a in good yields. Furthermore, the addition of tris(perfluoroalkyl)silylpropyl iodide afforded the corresponding pyridinium salt 8a excellently. The anion exchange of the resulting iodides gave the ionic liquids with high fluorophilicity.

Abstract The synthesis, aromaticity, and optical and electrochemical properties of zinc(II) complexes of 10,15,20‐triaryl‐15‐aza‐5‐oxaporphyrin (TriAAOP) were investigated. Metal‐templated cyclization of a zinc(II) 1,19‐dichloro‐5,10,15‐triaryl‐10‐azatetrapyrrin complex with an oxygen source afforded 20π TriAAOP in the neutral form. Oxidation of 20π TriAAOP with silver (I) hexafluorophosphate generated the 19π radical cation or 18π dication depending on the content of oxidant used. The interconversion between the three oxidation states (18π, 19π, and 20π) resulted in distinct changes in the aromaticity and optical properties of the 15‐aza‐5‐oxaporphyrin π‐system. Nuclear magnetic resonance spectroscopy of 20π TriAAOP revealed its antiaromatic character, whereas that of the 18π TriAAOP dication showed its aromatic character. The combined effect of the two meso‐heteroatoms was directly reflected in the redox properties of the porphyrin ring; TriAAOP was reduced more easily and more difficult to oxidize than the zinc(II) complex of 5,10,15,20‐tetraaryl‐5,15‐diaz‐aporphyrin (TADAP). In the ultraviolet‐visible‐near–infrared spectra of the materials, the lowest‐energy electronic excitations of the 19π and 18π TriAAOP derivatives were considerably red‐shifted compared with those of the isoelectronic TADAP derivatives. Based on the results of density functional theory calculations, it was concluded that the observed differences between TriAAOP and TADAP would arise from the high electronegativity of oxygen; specific frontier orbitals of the TriAAOP π‐systems were energetically stabilized relative to those of the TADAP π‐system. The present findings corroborate that the meso‐modification of a porphyrin rings with different kinds of heteroatoms is a promising strategy to fine tune their light‐response properties that are switchable by reversible single electron transfer processes.

Abstract New activated indolylpyrrolidones—their methylthiopyrrolinium salts—in the reactions with several CH‐acids were studied. 2‐Nitromethylene‐ and 2‐dicyanomethyleneindolylpyrrolidines were obtained from 5‐indolyl‐2‐methylthiopyrrolinium salts with good yields. The reduction in these nitro compounds yields the respective aminomethylpyrolidines. The rigid structure of the starting compounds has significant stereoelectronic requirements of nucleophilic agents.

Abstract New triorganotin(IV) derivatives of ciprofloxacin (HL) with general formula R3Sn(L) (where R = Me (1)/Cy (2) and L is the monoanion of ciprofloxacin) have been synthesized and structurally characterized on the basis of elemental analysis, IR, Raman, multinuclear (1H‐, 13C‐ and 119Sn‐) NMR, ESI‐MS, UV‐Visible, and emission spectroscopy. A distorted trigonal bipyramidal geometry around tin has been tentatively proposed for these triorganotin(IV) derivatives in which the ligand may act as monoanionic bidentate coordinating through the Ocarboxylate and Opyridone. The proposed structure has been validated by density functional theory (DFT)‐based electronic structure calculations at B3LYP/6‐31G(d,p)/Def2‐SVP(Sn) level of theory. The atomic charges have been calculated at the selected atoms, and the reactive sites have been assigned on the surface of the molecules through molecular electrostatic potential map. The frontier molecular orbitals and selected conceptual‐DFT‐based global reactivity descriptors have been calculated to obtain an insight into the structure and reactivity behavior of the complexes. A comparative analysis of the experimental vibrational frequencies and simulated harmonic frequencies indicates good correlation between them. The complexes were screened for their in vitro antibacterial activity against two Gram‐positive and five Gram‐negative bacterial strains. The results revealed that both the complexes exhibited promising antibacterial activity against the chosen strains (MIC: 0.062‐0.125 μg/mL).

Abstract Imidazo‐1,5‐alkynyl alcohol derivatives were synthesized, and they were cyclized to imidazo‐1,4‐oxazines by means of cesium carbonate. Propargyl‐allene isomerization was examined, and the reaction mechanism was proposed. Moreover, cytotoxicity of synthesized molecules against LN405 cell lines was investigated by means of structure‐activity relationship (SAR). With SAR study, toxicities of some functional groups have been shown. In addition, two lead compounds were tested against DNA damaging.

Abstract DFT calculations are applied to compare and contrast germanium atom(s) substituted C20‐nGen heterofullerenes with n = 1‐5, where the substitution is completely isolated from each other by means of one carbon atom in equatorial position. The structural stabilities, geometry, and electronic properties of C20 and its heterofullerene derivatives are compared and contrasted at M062X/6‐311++G**, B3LYP/AUG‐cc‐pVTZ, B3LYP/6‐311++G**, B3LYP/6‐311+G*, and B3PW91/6‐311++G** levels of theory. Vibrational frequency analysis shows that all of the heterofullerenes are real minima. Contrary to identical bonds in C20, contractions of C=C double bonds are encountered at the expense of longer C―Ge bonds in C20‐nGen. In contrast to previous reports on silicon doped heterofullerenes, none of the computed heterofullerenes collapses to open cage structures. Successive Ge doping on C20 induces more positive atomic charge on Ge atoms and more negative charge on C atoms. High charge transfer on the surfaces of our stable heterofullerenes provokes further investigations on their possible application for hydrogen storage. As to band gap, binding energy, heat of atomization per carbon, nucleus‐independent chemical shift, aromaticity, and the smallest vibrational frequency C19Ge immerges with the highest value. The reactivity in terms of ionization potential, nucleophilicity, electrophilicity, hardness, softness, maximum electronic charge, and proton affinity issues predicts C19Ge as the most stable heterofullerene against electronic excitation.