Methods for the synthesis of novel heterocyclic compounds bearing an unsaturated γ-lactone ring and an (S)-naproxen moiety were developed. The O-acylation reactions of 3,4-dihalo-5-hydroxy-2(5H)-furanones with (S)-(+)-2-(6-methoxy-2-naphthyl)propionyl chloride in the presence of Et3N afforded optically active furanone derivatives bearing an (S)-naproxen moiety at the 5 position of the lactone ring. Optically active 4-arylsulfanyl derivatives of 2(5H)-furanone were obtained by the reaction of the isolated (R,S) stereoisomers of 3,4-dihalofuranones with aromatic thiols. A series of heterocycles were synthesized based on 5-alkoxy- and 5-haloahkoxy-2(5H)-furanones containing an (S)-naproxen moiety in the side chain of the hydroxyethylthio substituent on the carbon atom C(4) of the five-membered ring. The structures of three new heterocycles were determined by X-ray diffraction.

A series of optically active 5(S)-(l-bornyloxy)- and 5(S)-(l-menthyloxy)-2(5H)-furanones with an arylthio group at the C(4) position of the γ-lactone ring was synthesized and studied for its oxidation reactions with various reagents. Novel 2(5H)-furanone sulfoxides were obtained as mixtures of two diastereoisomers through the oxidation of arylthioethers with m-chloroperbenzoic acid (m-СРВА) or hydrogen peroxide in acetic acid. Individual stereoisomers of these sulfoxides were isolated using recrystallization and high-performance liquid chromatography (HPLC) and characterized by IR and NMR spectroscopy. The molecular structures of eight stereoisomerically pure compounds were confirmed by X-ray diffraction (XRD) analysis. The antibacterial activity of the novel sulfoxides against Staphylococcus aureus and Escherichia coli was assessed, with a number of compounds found to inhibit bacterial growth and biofilm formation in S. aureus.

Allylboration of the 1,2,3-triazole and pyrazole aldehydes with triallylborane or 2,4-pentadienyl(dipropyl)borane under mild reaction conditions provides high yields of the corresponding novel homoallylic and dihomoallylic alcohols that can be used to modify the side chain in the triazole- or diazole-based molecules. Enantioselective allylboration of triazole aldehydes with (+)-B-allyldiisopinocampheylborane gave optically active R(+) homoallylic alcohols in good yields with 80–93

Novel disulfinyl derivatives based on 3,4-dichloro-2(5H)-furanone, aliphatic dithiols, and monoterpene alcohols were synthesized. Chiral bis-thioethers in the molecules of which the dithiol fragment links two five-membered cycles at C4 atoms were obtained in the reactions of 5(S)-(l-menthyloxy)- and 5(S)-(l-bornyloxy)-2(5H)-furanones with ethane-1,2-dithiol and propane-1,3-dithiol in acetone in basic medium. The action of an excess of m-chloroperoxybenzoic acid (2.0–3.2 equiv.) on bis-thioethers led to the formation of the corresponding mono- and disulfoxides bearing l-menthol or l-borneol fragments at the 5th position of the lactone ring. The methods of column chromatography and fractional recrystallization were used for the isolation of individual products. The structure of the synthesized heterocycles was proved by IR and NMR spectroscopy, and their composition was confirmed by high-resolution mass spectrometry. The molecular structure of the three disulfoxides was characterized by X-ray diffraction analysis.

Methods for the synthesis of novel optically active bisthioethers and disulfones of the furan-2(5H)-one series were developed. Bisthioethers with the dithiol fragment links two γ-lactone rings at the C4 atoms were synthesized by the reaction of 5(S)-(l-menthyloxy)- and 5(S)-(l-bornyloxy)furan-2(5H)-ones with ethane-1,2-dithiol and propane-1,3-dithiol in the presence of triethylamine. Chiral disulfones with a monoterpene alcohol fragment in the 5 position of the γ-lactone ring were obtained by the oxidation of the dithio furanone derivatives with hydrogen peroxide in acetic acid. The structure of five novel sulfur-containing furanone derivatives was characterized by single crystal X-ray diffraction.

The anionoid elimination of the substituent from position 5 of the lactone ring is the predominant pathway of electrochemical reduction of 5-arylsulfanyl- and 5-arylsulfonyl-3,4-dichloro-2(5H)-furanones in acetonitrile. The contribution of the competing elimination of the chloride ion increases on going to 3,4-dichloro-5-ethylsulfanyl-2(5H)-furanone. An experimental criterion based on the morphology of cyclic voltammograms was proposed for identification of a particular pathway of electroreduction of 2(5H)-furanone derivatives.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The macrocycles of large size have structural fratures and possess physical properties and chemical behavior different from their smaller analogues. The interest to these compounds is clue to their use as drugs, selective sensors, efficient transistors, organic light -emitting diodes, solar cells. Unfortunately; the entropy of the cyclization prevents the fOrmation ofsuch compounds because of the large number of monomeric units and significant flexibility gfacyclic oligomeric precursors, so they are very difficult to be synthesized. It is possible to allocate three approaches to the synthesis of "large macrocycles". One ofthem is based on the disclosure of macrocyclic ring of smaller macrocycles, the oligomerization and subsequent closure into lacrocycle..Another approach is a multicomponent niacrocyclization assembly), resulting in the formation of a large number of bonds simultaneously The main approach is a step-by-step synthesis. The examples of the synthesis of macrocyclic oligoanilines, oligopyridines, oligopyrroles, oligothiophenes, oligocarbazoles are known. Oligoaquinoxaline or oligoindolizine macrocycles have not been obtained. Step-by-step approach to the synthesis of the macrocycles containing 2" quinoxaline and indolizine structural units as a part of a macrocychc skeleton has been developed. The final stage of the synthesis of macrocycles involves intramolecular dehydrocychzation of the precursors which results in the formation of the carbon -carbon bond between indolizine fragments. Three-step oxidation of hiindolizine fragments are registered fir the macrocycles by CV,4 method. The first and third stages are reversible, and the second is irreversible. Oxidation at the potentials of the first peak leads to the stable cation-radicals registered by EPR method (g -2.0024, a, 0.26 MT). The fragmentation of macrocycles under the shooting conditions of MALDI mass-spectrometry measurements, unlike occurs with phenyl radical ejection from the charged molecules.

На основе ферроцен-1,1-диил-бисфосфиновых кислот Fc[P(R)(O)OH]2 (R = H, Me, Et, Ph) в метаноле создано два типа молекулярных роторов с электрохимическим двигателем. Моноанионы кислот за счет внутримолекулярной водородной связи фиксируются в цис-конформации, а дианионы за счет сил электростатического отталкивания – в транс-конформации. При переводе моноанионов в дианионы происходит управляемое вращение циклопентадиенильных колец из цис-конформации в транс-, а при обратном переключении происходит обратное вращение. В одном типе роторов вращение управляется обратимым изменением рН и состава раствора электрохимическим циклом окисления–ревосстановления N-фенил-N-изопропил-1,4-фенилендиамина, в другом типе – одноэлектронным окислением–ревосстановлением ферроценового ядра моноанионов. Последний тип ротора при комнатной температуре устойчиво функционирует только при малых временах ( < 1 c), при больших временах необратимо разрушается на стадии окисления.

Gram-positive bacteria cause a wide spectrum of infectious diseases, including nosocomial infections. While in the biofilm, bacteria exhibit increased resistance to antibiotics and the human immune system, causing difficulties in treatment. Thus, the development of biofilm formation inhibitors is a great challenge in pharmacology. The gram-positive bacterium Bacillus subtilis is widely used as a model organism for studying biofilm formation. Here, we report on the effect of new synthesized 2(5H)-furanones on the biofilm formation by B.subtilis cells. Among 57 compounds tested, sulfur-containing derivatives of 2(5H)-furanone (F12, F15, and F94) repressed biofilm formation at a concentration of 10 μg/ml. Derivatives F12 and F94 were found to inhibit the biosynthesis of GFP from the promoter of the eps operon encoding genes of the biofilm exopolysaccharide synthesis (EPS). Using the differential fluorescence staining of alive/dead cells, we demonstrated an increased bacterial sensitivity to antibiotics (kanamycin and chloramphenicol) in the presence of F12, F15, and F94, with F12 being the most efficient one. The derivative F15 was capable of disrupting an already formed biofilm and thereby increasing the efficiency of antibiotics.

The crystal structure of the known triclinic modification of mucochloric acid (MCA) was refined significantly, as well as its earlier unknown orthorhombic modification was discovered. In both forms, the compound is represented by two independent molecules with a pseudosymmetric relationship between them. Despite different symmetries of two crystal modifications of MCA, the triclinic centrosymmetric and rhombic chiral crystals display analogous layers formed by classical hydrogen bonds and stabilized additionally through the C–H...O and C=O...C=O (n(O)→π(C=O)*) interactions. The layers formally differ in the crystallographic status of symmetry elements: the triclinic crystal has crystallographic symmetry center, pseudosymmetric screw axes 2 1 , and pseudoplanes of sliding reflection; while, in the rhombic crystal, the axes 2 1 are crystallographic and the center of symmetry and glide planes are pseudosymmetric. The fundamental difference between the structures of polymorphs consists in the manner of layer joint: parallel in the triclinic crystal and antiparallel in the orthorhombic crystal. The triclinic crystal structure of mucobromic acid (MBA) isostructural to the well-known polymorph of MCA was established for the first time. The possible reason for the pseudosymmetry in the crystals of MCA and MBA is a specificity of the optimum geometry necessary for the Hal...Hal contacts to be realized, which results in the displacement of analogous layers relative to each other. The specific nature of Cl...Cl contacts in the MCA crystals was studied additionally by DFT/PBE0/6-31G(d,p).

Based on ferrocene-1,1'-diyl-bisphosphinic acids Fc[P(R)(O)OH] 2 (R = H, Me, Et, Ph) in methanol, two types of electrochemically driven molecular rotors are developed. Monoanions of acids are fixed in the cis-conformation due to the presence of an intramolecular hydrogen bond, whereas dianions are fixed in the trans-conformation due to electrostatic repulsion forces. Upon the transformation of monoanions to dianions, the controlled rotation of cyclopentadienyl rings from cis to trans-conformation occurs; the reverse switching leads to the reverse rotation. In one type of rotors, the rotation is controlled by the reversible variation of the solution pH and composition in the electrochemical oxidation-re-reduction cycle of N-phe-nyl-N'-isopropyl-1,4-phenylenediamine; in the other type, the rotation is determined by the one electron oxidation-re-reduction of the ferrocene nucleus in monoanions. The latter rotor type at room temperature can operate stably only for a short time (τ< 1 s) and at longer times is irreversibly destructed during the oxidation stage.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A number of 4- and 5-R-sulfanylfuran-2(5 H )-one derivatives were synthesized, and their oxidation with various reagents was studied. The corresponding sulfones were obtained using hydrogen peroxide in acetic acid. 4-R-sulfanyl derivatives were selectively oxidized to sulfoxides with m -chloroperoxybenzoic acid. The molecular and crystal structures of some new sulfones and sulfoxides were determined by X-ray analysis.

The X-ray diffraction study of cis -2,3-dichlorobuth-2-ene-1,4-diol ( 3 ) obtained by the reduction of 3,4-dichloro-5-ethoxy- and 5-isopropoxi-2(5 H )-furanones with lithium aluminum hydride is performed. The crystals of compound 3 are trigonal: a = b = 15.746(9) Å, c = 6.848(4) Å; V = 1470.5(15) Å 3 , space group P3 1 , Z = 9 (three independent molecules). Independent molecules have identical planar conformation, and hydroxyl groups are located on different sides of the multiple bond plane. The supramolecular motif of the crystal is spirals about the threefold screw axes; the neighboring spirals are linked by OH…O hydrogen bonds.

Crystallization of three 4-arylsulfonyl-2(5 H )-furanones from chloroform leads to the formation of a conglomerate of sulfone with para -tolyl substituent and racemic crystals of chloro and bromo analogs. The high degree of similarity of the crystal packings of a homochiral crystal and racemic compounds, viz. , the similar type of the homochiral hydrogen-bonded chains and analogous three-dimensional homochiral layers additionally stabilized by the interactions of the type C=O…C=O and C-H…O, allowed us to suggest the presence of the second, “missing” form for each sulfone. A directed search for the “missing” forms revealed the existence of the racemic modification of sulfone with the para -tolyl fragment formed during a very slow crystallization of the compound from benzene. No conglomerates of bromo and chloro analogs were found. Topological analysis of the electron density distribution performed by quantum chemical calculations using density functional theory (PBE1PBE, 6–31G(d,p)) showed the higher energy favorability of intermolecular interactions in the homochiral chains as compared to the hypothetical heterochiral associates.

5-Alkoxy-3-chloro-2(5 H )-furanones were synthesized by the electrochemical reduction of 5-alkoxy derivatives of mucochloric acid in acetonitrile on the lead electrode in the presence of acetic acid as a proton donor. A combined analysis of the experimental data and quantum chemical calculation of intermediates indicates the EE D C mechanism of reduction, including the tandem transfer of two electrons with chloride ion elimination at the stage of transfer of the second electron and protonation.