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Three bis- or tris-brominated 2-trifluoromethylquinolines have been successfully applied in palladium-catalysed Sonogashira reactions, leading to several examples of alkynylated quinolines in good to excellent yields. Optical properties of selected products have been studied by steady state absorption and fluorescence spectroscopy which give insights of the influence of the substitution pattern and of the type of substituents on the optical properties.

The development of a new and straightforward chemoselective method for the synthesis of uracil-based structures by combining Suzuki–Miyaura and Sonogashira–Hagihara cross-coupling is reported. The methodology was applied to synthesize a series of novel compounds. The tolerance of the combination of different functional groups was tested. The influence of different functional groups on the physical properties was studied by ultraviolet–visible (UV–vis) and fluorescence spectroscopy, providing new insights into the potential applications of uracil-based structures.

A new synthetic route to 1H-1,2,3-triazole-4,5-dithiols (tazdtH2) as ligands for the coordination of NiII, PdII, PtII and CoIII via the dithiolate unit is presented. Different N-protective groups were introduced with the corresponding azide via a click-like copper-catalyzed azide-alkyne [3 + 2] cycloaddition (CuAAC) and fully characterized by NMR spectroscopy. Possible isomers were isolated and an alternative synthetic route was investigated and discussed. After removal of the benzyl protective groups on sulfur by in situ-generated sodium naphthalide, complexes at the [(dppe)M] (M = Ni, Pd, Pt), [(PPh3)2Pt] and [(η5-C5H5)Co] moieties were prepared and structurally characterized by XRD analysis. In this process, the by-products 11 and 12 as monothiolate derivatives were isolated and structurally characterized as well. With regioselective coordination via the dithiolate unit, the electronic influence of different metals or protective groups at N was investigated and compared spectroscopically by means of UV/Vis spectroscopy and cyclic voltammetry. Complex [(η5-C5H5)Co(5c)] (10), is subject to a dimerization equilibrium, which was investigated by temperature-dependent NMR and UV/Vis spectroscopy (solution and solid-state). The thermodynamic parameters of the monomer/dimer equilibrium were derived.

Ullazines and their π-expanded derivatives have gained much attention as active components in various applications, such as in organic photovoltaic cells or as photosensitizers for CO2 photoreduction. Here, we report the divergent synthesis of functionalized diazaullazines by means of two different domino-reactions consisting of either a Povarov/cycloisomerization or alkyne–carbonyl metathesis/cycloisomerization protocol. The corresponding quinolino-diazaullazine and benzoyl-diazaullazine derivatives were obtained in moderate to good yields. Their optical and electronic properties were studied and compared to related, literature-known compounds to obtain insights into the impact of nitrogen doping and π-expansion.

2-Formylpyridine thiosemicarbazone - iron (III) chelates [FeL2] Cl•2H2O {L = L1 (C1) [HL1 = 4-(4-Nitrophenyl)-1-((pyridin-2-yl)methylene)thiosemicarbazide] and L = L2 (C2) [HL2 = 4-(2,5-Dimethoxyphenyl)-1-((pyridin-2-yl)methylene)thiosemicarbazide]} were prepared. The two ligand anions in each complex resulted in saturation of the iron coordination number and consequently the existence of these complexes as 1:1 electrolytes. As well, the iron in these complexes exhibits low-spin electronic configuration. X-ray crystallography of complex C1 indicated its triclinic crystal system and P 1‾ space group. In addition, it proved the ligation through a thiol sulfur atom and two nitrogen atoms of pyridine and azomethine groups. This is while the presence of two water molecules of crystallization in the complex structure was also indicated. The ligand HL1 was selected for cytotoxicity screening against human MCF-7, A-549, HEPG-2 and HCT-116 cancer cells and the most enhanced activities were detected against the breast cells. Against these cells, the compounds HL1, HL2, C1 and C2 induced cytotoxicity, respectively, with IC50 values of 52.4, 145.4, 34.3 and 62.0 μM. However, against the healthy BHK cells, HL1 and HL2 caused cytotoxicity, respectively, with IC50 values of 54.8 and 110.6 μM and cytotoxicity with percent viabilities of 56.7 and 55.4% of the BHK cells by the complexes (137.4 μM of C1 and 131.9 μM of C2) was determined. These activities against MCF-7 cells are less significant compared with the measured value for doxorubicin. But this standard is more toxic to normal cells than the thiosemicarbazones (IC50 (doxorubicin) = 9.66 μM against MCF-7 cells and 36.42 μM against BHK cells).

This article provides the first single-crystal XRD-based structure of enantiopure (R)-baclofen (form C), C10H12ClNO2, without any co-crystallized substances. In the enantiopure title compound, the molecules arrange themselves in an orthorhombic crystal structure (space group P212121). In the crystal, strong hydrogen bonds and C—H...Cl bonds interconnect the zwitterionic molecules.

Summary: Heterocyclobutane-1,3-diyls bridge the gap between organic and inorganic chemistry and are known for the majority of group 13–15 elements. The kinetically stabilized compounds have been employed in the activation of small molecules, akin to conventional transition metal complexes, and are thus cost-efficient alternatives for future processes. Here, we present the synthesis and characterization of a particularly unusual example of a heterocyclobutane-1,3-diyl, [RC(μ-NR′)2P], that blurs the line between biradical, zwitterion, and phosphinidene. While the reaction with AuCl and an NHC (N-heterocyclic carbene) shows resemblance to biradicals, the reaction with an alkyne to form a phosphirene is characteristic for phosphinidenes. Quantum chemical investigations allow for the classification of the amidinate-based heterocycle [RC(μ-NR′)2P] next to comparable literature examples.

New complexes of trivalent cobalt with substituted thiosemicarbazone ligands having an NNS donor system {HL1 = 4-(4-nitrophenyl)-1-((pyridin-2-yl)methylene)thiosemicarbazide and HL2 = 4-(2,5-dimethoxyphenyl)-1-((pyridin-2-yl)methylene)thiosemicarbazide} were synthesized via the in situ oxidation of divalent cobalt chloride accompanying its addition to the ligands. The complexes C1 and C2 were characterized via elemental (CHNS) analysis and 1H NMR, FT-IR and UV-Vis. spectroscopic data. Further, conductometric studies on the DMF solutions of the complexes indicated their 1:1 nature, and their diamagnetism revealed the low-spin trivalent oxidation state of the cobalt in the complexes. The X-ray diffraction analysis of complex C1 indicated that it crystallizes in the triclinic space group P-1. The metal exhibits an octahedral environment built by two anionic ligands bound via pyridine nitrogen, imine nitrogen and thiol sulfur atoms. The complex is counterbalanced by a chloride ion. In addition, two lattice water molecules were detected in the asymmetric unit of the unit cell. The ligand HL2 (20 mg/mL in DMSO) displayed inhibition zones of 10 mm against both S. aureus and E. coli, and the same concentration of the respective complex raised this activity to 15 and 12 mm against these bacterial strains, respectively. As a comparison, ampicillin inhibited these bacterial strains by 21 and 25 mm, respectively. Screening assay by HL1 on four human cancer cells revealed the most enhanced activity against the breast MCF-7 cells. The induced growth inhibitions in the MCF-7 cells by all compounds (0–100 μg/mL) have been detected. The ligands {HL1 and HL2} and complex C2 gave inhibitions with IC50 values of 52.4, 145.4 and 49.9 μM, respectively. These results are more meaningful in comparison with similar cobalt complexes, but less efficient compared with the inhibition with IC50 of 9.66 μM afforded by doxorubicin. In addition, doxorubicin, HL1 and HL2 induced cytotoxicity towards healthy BHK cells with IC50 values of 36.42, 54.8 and 110.6 μM, but surviving fractions of 66.1% and 62.7% of these cells were detected corresponding to a concentration of 100 μg/mL of the complexes (136.8 μM of C1 and 131.4 μM of C2).

A two-step palladium-catalyzed procedure based on Suzuki–Miyaura cross coupling, followed by a double Buchwald–Hartwig reaction, allows for the synthesis of pharmaceutically relevant benzo[4,5]furo[3,2-b]indoles in moderate to very good yield. The synthesized compounds have been analyzed with regard to their inhibitory activity (IC50) of nucleotide pyrophosphatases h-NPP1 and h-NPP3. The activity lies in the nanomolar range. The results were rationalized based on docking studies.

We show that carboxyl-functionalized ionic liquids (ILs) form doubly hydrogen-bonded cationic dimers (c+=c+) despite the repulsive forces between ions of like charge and competing hydrogen bonds between cation and anion (c+–a−). This structural motif as known for formic acid, the archetype of double hydrogen bridges, is present in the solid state of the IL 1−(carboxymethyl)pyridinium bis(trifluoromethylsulfonyl)imide [HOOC−CH2−py][NTf2]. By means of quantum chemical calculations, we explored different hydrogen-bonded isomers of neutral (HOOC–(CH2)n–py+)2(NTf2−)2, single-charged (HOOC–(CH2)n–py+)2(NTf2−), and double-charged (HOOC– (CH2)n−py+)2 complexes for demonstrating the paradoxical case of “anti-electrostatic” hydrogen bonding (AEHB) between ions of like charge. For the pure doubly hydrogen-bonded cationic dimers (HOOC– (CH2)n−py+)2, we report robust kinetic stability for n = 1–4. At n = 5, hydrogen bonding and dispersion fully compensate for the repulsive Coulomb forces between the cations, allowing for the quantification of the two equivalent hydrogen bonds and dispersion interaction in the order of 58.5 and 11 kJmol−1, respectively. For n = 6–8, we calculated negative free energies for temperatures below 47, 80, and 114 K, respectively. Quantum cluster equilibrium (QCE) theory predicts the equilibria between cationic monomers and dimers by considering the intermolecular interaction between the species, leading to thermodynamic stability at even higher temperatures. We rationalize the H-bond characteristics of the cationic dimers by the natural bond orbital (NBO) approach, emphasizing the strong correlation between NBO-based and spectroscopic descriptors, such as NMR chemical shifts and vibrational frequencies.

New pyranocoumarin and coumarin-sulfonamide derivatives were prepared and evaluated for their antioxidant, antimicrobial, and/or anti-inflammatory activities. Coumarin-sulfonamide compounds 8a–d demonstrated significant antioxidant activity, while 7c,d, 8c,d, and 9c,d exhibited antimicrobial activity equal to or higher than the standard antimicrobials against at least one tested microorganism. Regarding the anti-inflammatory testing, pyranocoumarins 2b, 3a,b and 5c and coumarin-sulfonamide compound 9a showed more potent antiproteinase activity than aspirin in vitro; however, five compounds were as potent as aspirin. The anti-inflammatory activity of the promising compounds was further assessed pharmacologically on formaldehyde-induced rat paw oedema and showed significant inhibition of oedema. For in vitro COX-inhibitory activity of coumarin derivatives, pyranocoumarin derivative 5a was the most selective (SI = 152) and coumarin-sulfonamide derivative 8d was most active toward COX-2 isozyme. The most active derivatives met the in silico criteria for orally active drugs; thus, they may serve as promising candidates to develop more potent and highly efficient antioxidant, antimicrobial, and/or anti-inflammatory agents.

The cyclization of cyclohexane-1,3-diones with various substituted pyridinium salts afforded functionalized 8-oxa-10-aza-tricyclo[7.3.1.02,7]trideca-2(7),11-dienes. The reaction proceeds by regioselective attack of the central carbon atom of the 1,3-dicarbonyl unit to 4-position of the pyridinium salt and subsequent cyclization by base-assisted proton migration and nucleophilic addition of the oxygen atom to the 2-position, as was elucidated by DFT computations. Fairly extensive screening of bases and additives revealed that the presence of potassium cations is essential for formation of the product.

In the title compound, C16H14ClFO3, the dihedral angle between the mean planes of the two benzene rings is 71.50 (5)°. Due to an intramolecular O—H...O hydrogen bond between the hydroxy group and the carbonyl O atom of the ethyl ester group, the ethyl ester group lies within the ring plane. The crystal structure is consolidated by intermolecular C—H...O and C—H...F interactions.

In the title compound, C17H17ClO4, the dihedral angle between the mean planes of the two benzene rings is 65.92 (5)°. The methyl ester group lies within the ring plane [deviations of O atoms from the plane = −0.051 (2) and 0.151 (2) Å] due to an intramolecular O—H...O hydrogen bond. In the crystal, molecules are held together by rather weak non-classical intermolecular C—H...O hydrogen bonds, resulting in dimeric units about inversion centers, forming eight- and ten-membered ring systems as R22(8) and R22(10) motifs.