E. K. Beloglazkina

Thiosulfonates: Synthesis, Reactions and Practical Applications

Abstract The present review covers basic work on the synthesis, chemical reactions and practical application of organic thiosulfonates published before 1969, and gives more detailed attention to papers which appeared in the literature during the last 20 years. Three approaches to the synthesis of thiosulfonates, namely, (i) oxidation-reduction techniques, (ii) nucleophilic and, (iii) electrophilic introduction of an RSO2S moiety into an organic substrate, are presented in this review. (The synthetic part is divided into two subchapters: the synthesis of “symmetric” thiosulfonates and of “unsymmetric” ones). Nucleophilic substitution, electrophilic reactions, thermolysis and photolysis of thiosulfonates are also described. A special chapter serves as a brief summary of some practical applications of thiosulfonates.

Mixed Valence Copper(I,II) Binuclear Complexes with Unexpected Structure: Synthesis, Biological Properties and Anticancer Activity

We have synthesized and characterized a panel of new binuclear mixed valence Cu(I,II) complexes containing substituted 2-alkylthio-5-arylmethylene-4H-imidazolin-4-ones with unusual structure. These complexes are shown to be cytotoxic for various cell lines. We have found that these compounds did not intercalate DNA, inhibited number of polymerases (telomerase predominantly), accumulated in the cell nucleus, and caused DNA degradation. Preliminary studies revealed that lead compound inhibited human breast adenocarcinoma growth in mice model.

Design, synthesis and biological evaluation of novel potent MDM2/p53 small-molecule inhibitors.

Regioselective synthesis, biological evaluation and 3D-molecular modeling for a series of novel diastereomeric 2-thioxo-5H-dispiro[imidazolidine-4,3-pyrrolidine-2,3-indole]-2,5(1H)-diones are described. The studied compounds have been tentatively identified as potent small molecule MDM2/p53 PPI inhibitors and can therefore be reasonably regarded as promising anticancer therapeutics.

Enzyme-functionalized gold-coated magnetite nanoparticles as novel hybrid nanomaterials: Synthesis, purification and control of enzyme function by low-frequency magnetic field

The possibility of remotely inducing a defined effect on NPs by means of electromagnetic radiation appears attractive. From a practical point of view, this effect opens horizons for remote control of drug release systems, as well as modulation of biochemical functions in cells. Gold-coated magnetite nanoparticles are perfect candidates for such application. Herein, we have successfully synthesized core-shell NPs having magnetite cores and gold shells modified with various sulphur containing ligands and developed a new, simple and robust procedure for the purification of the resulting nanoparticles. The carboxylic groups displayed at the surface of the NPs were utilized for NP conjugation with a model enzyme (ChT). In the present study, we report the effect of the low-frequency AC magnetic field on the catalytic activity of the immobilized ChT. We show that the enzyme activity decreases upon exposure of the NPs to the field.

A convenient method for bromosulfenylation: Reactions of sulfenamides with olefins in the presence of POBr3

Abstract A general method for the one-pot transformation of alkenes into abromoalkyl-arylsulfdes has been proposed based on the sulfenylation reaction by means of sulfenamides in the presence of phosphorus oxibromide. The plausible reaction mechanism and the results of reactions with a number of model alkenes such as cyclohexene, I-heptene, norbornene and other from the bicyclo[2.2.1] heptane series are discussed.

Organic chemistry. History and mutual relations of universities of Russia

The review describes the history of development of organic chemistry in higher schools of Russia over a period of 170 years, since the emergence of organic chemistry in our country till now.

Coordination Compounds of S- and Se-Containing Organic Ligands as Catalysts of Oxidation Reaction Under N2O Action

Abstract Nitrous oxide (N2O) would be preferable to many other oxidants because in the reactions of N2O with organic compounds the only byproduct is N2, which is perfect from the point of view of “green” chemistry. We recently reported a series of new sulfur- and selenoorganic ligands, their coordination compound with Co(II) or Cu(I,II), and the possibility for these complexes to activate nitrous oxide in the oxidation reactions with phosphines and alkenes. The electrochemical data confirm the stability of reduced form of investigated complexes and the capacity of these complexes to associate with nitrous oxide. GRAPHICAL ABSTRACT

Formation of CuI(CH3CN)4ClO4 in the reactions of copper(II) perchlorate with acetonitrile in the presence of sulfur-containing organic compounds

Cu(ClO4)2·6H2O was shown to react with 2,2′-[propane-1,3-diylbis(thio-2-phenylnemethylidene]-bis(3-pyridylamine) (I) or (5Z)-2-ethoxycarbonylmethyl-(2-pyridylmethylidene)-3,5-dihydro-4H-imidazol-4-one (II) in the presence of CH3CN with the reduction of copper(II) to copper(I) and the formation of the tetrahedral complex CuI(CH3CN)4ClO4 (III). In the course of the reaction the organic ligands I and II were oxidized to the corresponding sulfoxides.

Small-molecule PSMA ligands. Current state, SAR and perspectives.

Abstract Prostate cancer (PC) is the prevalent malignancy widespread among men in the Western World. Prostate specific membrane antigen (PSMA) is an established PC marker and has been considered as a promising biological target for anti-PC drug delivery and diagnostics. The protein was found to be overexpressed in PC cells, including metastatic, and the neovasculature of solid tumors. These properties make PSMA-based approach quite appropriate for effective PC imaging and specific drug therapy. Through the past decade, a variety of PSMA-targeted agents has been systematically evaluated. Small-molecule compounds have several advantages over other classes, such as improved pharmacokinetics and rapid blood clearance. These low-weight ligands have similar structure and can be divided into three basic categories in accordance with the type of their zinc-binding core-head. Several PSMA binders are currently undergoing clinical trials generally for PC imaging. The main goal of the present review is to describe the recent progress achieved within the title field and structure activity relationships (SAR) disclosed for different PSMA ligands. Recent in vitro and in vivo studies for each type of the compounds described have also been briefly summarized.

Structure determination of bis{(4Z)-1-(2-azidoethyl)-4-[(pyridin-2-yl)methylidene]-2-thiolatoimidazol-5(4H)-one}dicopper chloride from X-ray powder diffraction data

The new tridentate organic N2S-type ligand, (4Z)-1-(2-azidoethyl)-4-[(pyridin-2-yl)-methylidene]-2-thioxoimidazol-5(4H)-one (LH), was synthesized. The reaction of LH with copper(II) chloride in a CH2Cl2/MeOH mixture afforded the coordination compound of the composition L2Cu2Cl (3). The crystal structure of 3 was solved and refined from X-ray powder diffraction data. Complex 3 has a binuclear structure with a short interatomic Cu-Cu distance and one bridging chlorine atom, which is located almost symmetrically with respect to both metal atoms. The planar organic ligands are noncoplanar and are at an angle of 53.56(1)° to each other.