One-Pot Reductive Methylation of Nitro- and Amino-Substituted (Hetero)Aromatics with DMSO/HCOOH: Concise Synthesis of Fluorescent Dimethylamino-Functionalized Bibenzothiazole Ligands with Tunable Emission Color upon Complexation.

One-pot reductive N,N-dimethylation of suitable nitro- and amino-substituted (hetero)arenes can be achieved using a DMSO/HCOOH/Et3N system acting as a low-cost but efficient reducing and methylating agent. The transformation of heteroaryl-amines can be accelerated by using dimethyl sulfoxide/oxalyl chloride or chloromethyl methyl sulfide as the source of active CH3SCH2+ species, while the exclusion of HCOOH in the initial stage of the reaction allows avoiding N-formamides as resting intermediates. The developed procedures are applicable in multigram-scale synthesis, and because of the lower electrophilicity of CH3SCH2+, they also work in pathological cases, where common methylating agents provide N,N-dimethylated products in no yield or inferior yields due to concomitant side reactions. The method is particularly useful in one-pot reductive transformation of 2-H-nitrobenzazoles to corresponding N,N-dimethylamino-substituted heteroarenes. These, upon Cu(II)-catalyzed oxidative homocoupling, afford 2,2'-bibenzazoles substituted with dimethylamino groups as charge-transfer N^N ligands with intensive absorption/emission in the visible region. The fluorescence of NMe2-functionalized bibenzothiazoles remains intensive even upon complexation with ZnCl2, while emission maxima are bathochromically shifted from the green/yellow to orange/red spectral region, making these small-molecule fluorophores, exhibiting large emission quantum yields and Stokes shifts, an attractive platform for the construction of various functional dyes and light-harvesting materials with tunable emission color upon complexation.

Diastereoselective Double C-H Functionalization of Chiral Ferrocenes with Heteroaromatics.

Diastereoselective double C-H heteroarylation of chiral ferrocenes provides valuable compounds with multiple functionalities using mild reaction conditions and simple reagents. Pd-Complexes with chiral mono-protected amino acids afforded corresponding heteroarylated ferrocenyl amines in good yields and high diastereomeric purities. In this way, a variety of indole, thiophene, pyrrole, or furan substituents were introduced to the ferrocene moiety. Furthermore, a range of relevant functional groups, for example ketone, ester, chloro, nitro, or silyl, are tolerated by this method. An alternative combination of amino acid and ferrocenyl amine configurations was leveraged to provide the complementary diastereomeric products. The products of C-H heteroarylation can be transformed into corresponding phosphines. Absolute configurations of CH-activation products were confirmed by the combination of X-ray crystallographic analysis and CD spectroscopy. 19 F NMR kinetic study and DFT calculations provided insights into the reaction mechanism and reasons governing stereoinduction.

Diastereoselective Pd-Catalyzed C-H Arylation of Ferrocenylmethanamines with Arylboronic Acids or Pinacol Esters.

An efficient diastereoselective synthesis of planar chiral ferrocenes via Pd(II)-catalyzed direct C-H activation with arylboronic acids or pinacol esters is presented. The reaction was performed under mild conditions using commercially available achiral or chiral amino acids as ligands. The best results were obtained with ( R)-Boc-alanine, which yielded products in 27-83% yield with diastereoselectivities ranging from 5:1 to 20:1 (11 examples). Diastereoisomeric products can also be obtained using ( S)-Boc-alanine as a ligand. Stereoinduction of the reaction was explained by density functional theory calculations of possible transition states.

catena-Poly[[(pyrazine-2-carboxamide-κN (4))copper(I)]-µ3-iodido].

In the title metal-organic polymeric complex, [CuI(C5H5N3O)] n , the asymmetric unit is composed of one monomer unit of the polymer and one Cu(I) atom linked to one iodide anion and one pyrazine-2-carboxamide mol-ecule. The Cu(I) atom is in a distorted tetra-hedral coordination completed by one pyrazine N atom of the pyrazine-2-carboxamide ligand and three iodide anions. The polymeric structure adopts a well-known ladder-like motif of {CuNI3} tetra-hedra running in the b-axis direction. The mol-ecules of the organic ligand are connected via medium-to-strong N-H⋯O and N-H⋯N hydrogen bonds and weak π-π inter-actions [the distance between two parallel planes of the rings is 3.5476 (14) Šand the centroid-centroid contact is 4.080 (2) Å]. The title compound has a relatively high decomposition temperature (564 K) as a result of relatively strong covalent and non-covalent inter-actions inside and between the chains.

Tetrakis(2,6-di-methyl-pyridinium) di-hydrogen deca-vanadate dihydrate.

The structure of the title compound, (C7H10N)4[H2V10O28]·2H2O, was solved from a non-merohedrally twinned crystal (ratio of twin components ∼0.6:0.4). The asymmetric unit consists of one-half deca-vanadate anion (the other half completed by inversion symmetry), two 2,6-di-methyl-pyridinium cations and one water mol-ecule of crystallization. In the crystal, the components are connected by strong N-H⋯O and O-H⋯O hydrogen bonds, forming a supra-molecular chain along the b-axis direction. There are weak C-H⋯O inter-actions between the chains.

Organocatalytic Diastereodivergent Enantioselective Formal oxa-Diels-Alder Reaction of Unsaturated Ketones with Enoates Under Liquid-Assisted Grinding Conditions.

Chiral heterocycles occur in many compounds of interest, but their efficient synthesis is challenging. This study concerns the enantioselective and diastereoselective synthesis of densely substituted chiral pyran derivatives. Diastereodivergence of the oxa-Diels-Alder reaction is achieved by using either a bifunctional amino-thiourea or a monofunctional quinine organocatalyst under ball-milling conditions. Liquid-assisted grinding proves a highly efficient means of affording pyrans in high yield, with high enantiomeric purities and short reaction times.

Direct Iodination of Electron-Deficient Benzothiazoles: Rapid Access to Two-Photon Absorbing Fluorophores with Quadrupolar D-π-A-π-D Architecture and Tunable Heteroaromatic Core.

Direct iodination of benzothiazoles under strong oxidative/acidic conditions leads to a mixture of iodinated heteroarenes with 1-2 major components, which are easily separable and which structures depend on the I2 equivalents used. Among the unexpected but dominant products were identified 4,7-diiodobenzothiazoles with a rare substitution pattern for SEAr reactions of this scaffold. These were employed in the synthesis of 4,7-bis(triarylamine-ethynyl)benzothiazoles - a new class of highly efficient quasi-quadrupolar fluorophores displaying large two-photon absorption cross sections (540-1374 GM) in the near-infrared region.

Bis[2-(2-hydroxyethyl)pyridinium] mu-decavanadato-bis[pentaaquamanganate(II)] tetrahydrate.

The structure of the title compound, (C(7)H(10)NO)(2)[Mn(2)V(10)O(28)(H(2)O)(10)].4H(2)O or (C(5)H(4)NHCH(2)CH(2)OH)(2)[{Mn(H(2)O)(5)}(2)V(10)O(28)].4H(2)O, at 293 (2) K has triclinic (P\overline{1}) symmetry. The asymmetric unit consists of one half of a decavanadate anion of C(i) symmetry, one [Mn(H(2)O)(5)](2+) group, one 2-(2-hydroxyethyl)pyridinium cation and two solvent water molecules. The decavanadate ion bridges between two [Mn(H(2)O)(5)](2+) groups, thus forming a dodecanuclear complex unit. Complex units are connected via a hydrogen-bonding network, forming supramolecular layers lying in the (001) plane. Cations and solvent water molecules are located between these layers.

Quadrupolar benzobisthiazole-cored arylamines as highly efficient two-photon absorbing fluorophores.

A computer-aided design of novel D-π-A-π-D styrylamines containing five isomeric benzobisthiazole moieties as the electron-accepting core has revealed the linear centrosymmetric benzo[1,2-d:4,5-d']bisthiazole as the most promising building block for engineering chromophores displaying high two-photon absorption (TPA) in the near-IR region, as also confirmed experimentally. The ease of synthesis of quadrupolar derivatives thereof, combined with extraordinarly high TPA action cross sections (δTPAΦf > 1500 GM), makes these heteroaromatic systems particularly attractive as diagnostic agents in 3D fluorescence imaging.

In situ photoexcitation of silver-doped titania nanopowders for activity against bacteria and yeasts.

Photocatalytic and in situ microbial activity of the amorphous and annealed states of Ag-doped and un-doped titania were examined. Studies on their structure, morphology, composition, and the photo-absorption characteristics of these materials were performed. These results were correlated with the photocatalytic and microbial activity against methicillin resistant Staphylococcus aureus K324 (MRSA), methicillin susceptible S. aureus ATCC 25923 (MSSA), Escherichia coli PA 170, and yeasts Candida albicans ATCC 90028. The annealed powders containing anatase form of titania exhibited relatively higher photocatalytic activity,corresponding to activity against MRSA,when exposed to UV-A radiation. In comparison, amorphous powders exhibited low photoactivity and showed poor antibacterial performance against MRSA under UV-A exposure. Doping of amorphous titania with Ag resulted in an anti-MRSA effect without exposure to UV radiation. In the Ag-doped crystalline anatase samples, the size of Ag primary nanocrystallites increased, which led to the decrease in the surface concentration of Ag and detriment anti-MRSA activity.

Formulating fluticasone propionate in novel PEG-containing nanostructured lipid carriers (PEG-NLC).

The aim of this study was to develop nanostructured lipid carriers (NLC) for topical delivery of fluticasone propionate (FP) with the aim to further improve the safety profile and decrease the adverse-side effects commonly reported in topical corticotherapy. NLC are colloidal drug-carriers consisting of a blend of a solid lipid and a small amount of liquid lipid since these carriers have proved to be effective in epidermal targeting in particular of glucocorticoids. NLC consisting of glyceryl palmito-stearate, and PEG-containing medium chain triglycerides mixture, stabilised by polysorbate 80 and soybean phosphatidylcholine were prepared. A mean particle size between 380 and 408 nm and entrapment efficacy of 95% were obtained for FP-loaded NLC. The crystallinity and polymorphic phase behaviour of FP-free and FP-loaded NLC were examined by differential scanning calorimetry and wide angle X-ray diffraction. Results revealed a low-crystalline structure and confirmed the incorporation of FP into the particles. The suitability of PEG-containing liquid lipids to form the lipid matrix of NLC was also confirmed.

Hexakis[3-(aminocarbonyl)pyridinium] decavanadate(V) dihydrate.

The structure of the title compound, (C(6)H(7)N(2)O)(6)[V(10)O(28)].2H2O, at 120 (2) K has monoclinic (C2/c) symmetry. The asymmetric unit consists of one half-decavanadate anion of Ci symmetry, three cations and one water molecule. Each water molecule is hydrogen bonded to two decavanadate anions, thus forming a one-dimensional chain of anions. The three-dimensional supramolecular structure is formed by a network of N-H...O, O-H...O and C-H...O hydrogen bonds, in which the cations, anions and water molecules are involved, and by nonparallel-displaced pi-stacking interactions between pyridine rings. As a result of hydrogen bonding, the carboxamide groups of the cations are somewhat twisted from the pyridine ring plane.