E. I. Troyanskii

Abstract: 1. During the oxidative cyanation of 2-, 3-, and 4-methylcyclohexanones in the Na2S2O8-NaCN system the corresponding 4-cyano(methyl)cyclohexanones are formed regiospecifically. 2. The oxidative cyanation of 2- and 3-methylcyclohexanones takes place diastereoselectively with the formation of trans- and cis-4-cyano-2(3)-methylcyclohexanones in a ratio of 1.5∶1 (or 2∶1). The selectivity of cyanation is determined by the bridge structure of the intermediate 4-oxo(methyl)cyclohexyl radicals, which are the precursors of the 4-cyanocyclohexanones.

Abstract: The homolytic heterocyclization of dialkyl- and diaryl-acetylenes with 1,2-ethanedithiol leads stereoselectively to cis-2,3-disubstituted 1,4-dithianes. The stereochemistry of the reactions is determined by a combination of homolytic trans addition at the triple bond and intramolecular homolytic cis addition at the double bond. The main product of the heterocyclization of dimethyl acetylenedicarboxylate is dimethyl 5,6-dihydro-1,4-dithiin-2,3-dicar-boxylate.

Abstract: A single stage remote oxidation of ketones to γ- and δ-diketones has been carried out in a sodium peroxysulfate-iron(II) sulfate system.

Abstract: 1. In the Na2S2O8-CuCl2 system, secondary aliphatic amines (RCH2CH2)2NH are transformed into 2-chloro- and 2,2-dichloroalkanals, alkanoic acids and their alkylamides; their most probable precursors are RCH2CH=NCH2CH2R azomethines, formed as a result of oxidative deprotonation. 2. In the Na2S2O8-NaCN-NaOH system, oxidation of dialkylamines by a mechanism of oxidative substitution with the formation of the products of N-cyanidation: cyanamides and ureas, and the products of N-hydroxylation, dialkylhydroxylamines, predominate.

Abstract: 1. The azacycloalkanes HNCH2(CH2)nCH2CH2 (n=1–3), on treatment with the Na2S2O8-NaCN-NaOH system, undergo the competing reactions of N-cyanation to give the ureas, C-cyanation to give 2-cyanoazacycloalkanes, and β-fragmentation to give N-cyanomethyl- and N-formylazacycloalkanes. The relative proportions of these three competing reactions depend on the size of the ring. 2. Oxidative β-fragmentation of azacycloalkanes also occurs in the K3Fe(CN)6-NaOH and Na2S2O8-AgNO3-NaOH systems.

Abstract: A compound is represented by Structural Formula (I), or a pharmaceutically acceptable salt thereof, wherein the variables of Structural Formula (I) are as described in the specification and the claims. A pharmaceutical composition comprises a compound represented by Structural Formula (I) or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier of excipient. A method of treating a HCV infection in a subject comprises administering to the subject a therapeutically effective amount of a compound represented by Structural Formula (I) or a pharmaceutically acceptable salt thereof. A method of inhibiting or reducing the activity of HCV polymerase in a subject or in a biological in vitro sample comprises administering to the subject or to the sample a therapeutically effective amount of a compound represented by Structural Formula (I) or a pharmaceutically acceptable salt thereof.

Abstract: Sodium periodate (NaIO4) is shown to be a milder and more efficient terminal oxidant for C–H oxidation with Cp*Ir (Cp* = C5Me5) precatalysts than ceric(IV) ammonium nitrate. Synthetically useful yields, regioselectivities, and functional group tolerance were found for methylene oxidation of substrates bearing a phenyl, ketone, ester, or sulfonate group. Oxidation of the natural products (−)-ambroxide and sclareolide proceeded selectively, and retention of configuration was seen in cis-decalin hydroxylation. At 60 °C, even primary C–H bonds can be activated: whereas methane was overoxidized to CO2 in 39% yield without giving partially oxidized products, ethane was transformed into acetic acid in 25% yield based on total NaIO4. 18O labeling was demonstrated in cis-decalin hydroxylation with 18OH2 and NaIO4. A kinetic isotope effect of 3.0 ± 0.1 was found in cyclohexane oxidation at 23 °C, suggesting C–H bond cleavage as the rate-limiting step. Competition experiments between C–H and water oxidation show tha...

Abstract: Thermodynamic measurements were made for the binary mixture of water + γ-valerolactone (GVL) and for pure GVL to facilitate the development of the technology of lignin removal from lignocellulosic biomass (Fang, W.; Sixta, H. Advanced Biorefinery based on the Fractionation of Biomass in γ - Valerolactone and Water. ChemSusChem 2015, 8, 73−76). The density and vapor pressure of pure GVL as a function of temperature were measured and correlated for a wide range of the temperatures and pressures. Isothermal vapor–liquid equilibrium (VLE) data of the binary mixture of water + GVL were measured at 350.2 K with a static total pressure apparatus. Absence of an azeotrope was confirmed by circulation still measurements with diluted GVL solutions. Excess molar enthalpy (hE) of the mixture for the whole range of mole fractions including infinite dilution was measured using a SETARAM C80 calorimeter equipped with a flow mixing cell at 322.6 and 303.2 K. The VLE and hE data were used for the optimization of UNIQUAC an...

Abstract: Trivalent copper complexes are active intermediates in aquatic redox reactions that involve copper ions or structural copper, but their reactivity and selectivity toward pollutants remain unknown. We characterized copper(III) periodate, a representative trivalent copper compound, with phenol and several antibiotics as model contaminants. The results show that Cu(III) is highly reactive to phenol degradation; near-complete degradation was achieved after 10 min at a molar ratio of 3:1 (Cu[III]: phenol). Common alcohols, including methanol and 2-propanol, showed pH-dependent reactivity for Cu(III). In contrast to aquo trivalent copper ions that react rapidly with tert-butanol, Cu(III) showed limited reactivity toward tert-butanol. A mechanistic investigation showed that the degradation was caused by direct oxidation by Cu(III) and that no hydroxyl radicals were involved. Common water components such as chloride ions did not influence the reaction, which suggests that the use of Cu(III) may help mitigate the generation of chlorinated products. As a one-electron oxidant, Cu(III) showed high reactivity to degrade electron-rich compounds; the concentrations of sulfamethazine, sulfamethoxazole, and sulfadiazine (100 μg/L) were reduced to 1.8, 7.5, and 42.5 ng/L, respectively, after 2 min of reaction with 10 μM Cu(III). These results demonstrate a novel and highly efficient oxidant for selective removal of ubiquitous micropollutants from water bodies.