The presence of dimethylacetamide (DMAA) in the composition of electrolytes of a sodium-ion battery destroys the passive film on electrodes and results in a number of reactions not connected with the electrochemical process that must be considered in developing such batteries. Introducing DMAA into the composition of a battery electrolyte greatly improves the conductivity of the polymeric membrane that separates the cathode and anode spaces. However, it is established that in the presence of sodium metal, anhydrous DMAA undergoes Claisen-like self-condensation with subsequent reactions. IR spectroscopy is used to explain the causes of the electrochemical instability of sodium perchlorate solutions in mixed solvents containing DMAA.

New 3,20-dihydroxy-13 alpha-19-norpregna-1,3,5(10)-trienes were synthesized. The effects of these compounds on breast cancer cells and ER alpha activation were investigated. The scaffold of compounds containing the six-membered ring D' annulated at 16 alpha,17 alpha-positions was constructed via the Lewis acid catalyzed Diels-Alder reaction of butadiene with 3-methoxy-13 alpha-19-norpregna-1,3,5(10),16-tetraen-20-one 5 under a pressure of 600 MPa. The hydrogenation of primary cyclohexene adduct 6 followed by the one-pot reduction demethylation (DIBAH) gave target epimeric 3,20-dihydroxy steroids 8a and 8b. The Corey-Chaykovsky reaction of the same conjugated ketone 5 gave a 16 alpha,17 alpha-methylene-substituted compound. The reaction of the latter with DIBAH yielded 3,20(R,S)-dihydroxy-16 alpha,17 alpha-methyleno-13 alpha-19-norpregna1,3,5(10)-triene 10. The hydrogenation of the 16,17-double bond of compound 5 produced a mixture of 17 alpha and 17 beta-epimeric ketones, reduction demethylation of which gave 3,20(S)-dihydroxy-13 alpha,17 alpha-19-norpregna-1,3,5(10)-triene 12a and 3,20(R)-dihydroxy-13 alpha,17 beta-19-norpregna-1,3,5(10)-triene 12b. All compounds were fully characterized by 1D and 2D NMR, HRMS, and X-ray diffraction. All target compounds showed pronounced cytotoxic effect against MCF-7 breast cancer cells and NCI/ADR-RES doxorubicin-resistant cells at micromolar concentrations. The ER alpha-mediated luciferase reporter gene assay demonstrated that all compounds, except for compound 10, are ER alpha inhibitors, while cyclopropane compound 10 proved to be an ER alpha activator. Docking experiments showed that all compounds are well accommodated to LBD ER alpha but have some differences in the binding mode.

Racemic Albicar (2,6-diethyl-4,8-dimethylglycoluril) has been synthesized and resolved into enantiomers on a preparative scale by chiral HPLC. A comparison of the pharmacological effects of these compounds has been performed for the first time. It has been demonstrated that the (−)-(1S,5S)-enantiomer exerts a stimulating effect on the central nervous system due to activation of the serotonergic system, since it potentiates the effects of 5-hydroxytryptophan (the serotonin precursor), while the antagonist of serotonin receptors blocks its activity; the (+)-(1R,5R)-enantiomer evinces an inhibitory effect.

A series of polyalkoxy substituted 7-hydroxy- and 7-methoxy-4-aryl-4H-chromenes were evaluated using the sea urchin embryo model to yield several compounds exhibiting potent antimitotic microtubule destabilizing activity. Data obtained by the assay were further confirmed in the NCI60 human cancer cell screen. The replacement of methylenedioxy ring A and lactone ring D in podophyllotoxin analogues by 7-methoxy, 2-NH2, and 3-CN groups in 4-aryl-4H-chromenes resulted in potent antimitotic microtubule destabilizing agents. Feasible synthesis and high yields render 7-methoxy-4H-chromenes to be a promising series for further anticancer drug development.

A series of 4H-chromenes containing various modifications in the ring B and polyalkoxy substituents in the ring E has been synthesized by Knoevenagel-Michael-hetero-Thorpe-Ziegler three-component domino reaction with the overall yield of 45-82%. The targeted molecules were evaluated in a phenotypic sea urchin embryo assay for antimitotic and microtubule destabilizing activity. The most active compounds 5{1,5} and 5{5,5} featured sesamol-derived ring B and m-methoxyphenyl or m-methoxymethylenedioxyphenyl ring E. Compounds 5{3,1}, 5{1,2}, 5{5,4}, 5{1,5}, and 5{5,5} exhibited strong cytotoxicity in the NCI60 human tumor cell line anticancer drug screen. Surprisingly, cell growth inhibition caused by these agents was more pronounced in the multidrug resistant NCI/ADR-RES cells than the parent OVCAR-8 cell line. The results suggest that polyalkoxy substited 4H-chromenes may prove to be advantageous for further design as anticancer agents.

A series of 4-azapodophyllotoxin derivatives with modified rings B and E have been synthesized using allylpolyalkoxybenzenes from parsley seed oil. The targeted molecules were evaluated in vivo in a phenotypic sea urchin embryo assay for antimitotic and tubulin destabilizing activity. The most active compounds identified by the in vivo sea urchin embryo assay featured myristicin-derived ring E (4e, 6e, and 8e). These molecules were determined to be more potent than podophyllotoxin. Cytotoxic effects of selected molecules were further confirmed and evaluated by conventional assays with A549 and Jurkat human leukemic T-cell lines including cell growth inhibition, cell cycle arrest, cellular microtubule disruption, and induction of apoptosis. The ring B modification yielded 6-OMe substituted molecule 8e as the most active compound. Finally, in Jurkat cells, compound 8e induced caspase-dependent apoptosis mediated by the apical caspases-2 and -9 and not caspase-8, implying the involvement of the intrinsic caspase-9-dependent apoptotic pathway.

Asymmetric hydrogenation of the C=C bond in 5-acetylamino-5-phenylpent-4-enoic acid methyl ester or N,N-dimethylamide catalyzed by rhodium complexes with chiral bisphosphine ligands (1 mol.% of the catalyst, 20 atm. of H2, MeOH, 50 °C) gives the corresponding saturated derivatives with enantioselectivity up to 40% ??.

Atropisomeric naphthalene proton sponges (R,S)-3 (meso), (R,R + S,S)-3 (racemic) and (S,S)-3 (enantiopure) were prepared by bis-N,N-dialkylation of 1,8-diaminonaphthalene, using both racemic (R + S)- and enantiopure (S)-2,2′-bis(bromomethyl)-1,1′-binaphthyl, respectively, as alkylating agents. The amino function of the corresponding mono-binaphthyl substituted tertiary/primary diamines (R + S)-4 (racemic) and (S)-4 (enantiopure), obtained as side products, was N,N-dimethylated to give the corresponding bis(tertiary) diamines (R + S)-2 and (S)-2, respectively. Thermal isomerisation of the meso adduct (R,S)-3 to the corresponding racemic adduct (R,R + S,S)-3 occurred in the solid state. Reversible evolution of the 1H NMR spectra of (R,S)-3, (R,R + S,S)-3 and (R + S)-2 in toluene-d8 solution as a function of temperature was observed, showing conformational changes but no isomerisation of the binaphthyl skeleton. 1H NMR of the protonated diamines showed the resonance of a single proton at very low field (18.7–20.2 ppm) in all cases.

Tetrahydrofurfurylamine enantiomers were separated on a preparative scale by fractional crystallization of diastereoisomeric salts with natural L-tartaric acid. (R)-Tetrahydrofurfurylamine was isolated in 68% yield with an optical purity of more than 98.5% according to the HPLC data.

Bis-ortho-methyl-bis-meta-bromo Tröger base (TB) 2 and bis-ortho-methyl TB 3 were prepared in enantiopure form. The absolute configuration for (5S,11S)-(−)-2 was determined by X-ray diffraction. The sign of the longest wavelength band in the electronic CD spectrum is negative for both (5S,11S)-(−)-2 and (5S,11S)-(−)-3, as well as for the parent para-methyl TB (5S,11S)-(+)-1, which is in agreement with TD DFT B3LYP/6-31G(d,p) calculations.

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 three-step synthesis of adduct 3 has been reinvestigated; enantiomers 3a and 3b have been separated by enantio selective chromatography and the racemization barrier of 3a was determined as DeltaG(not equal) = 24.4 kcal mol(-1) (16 degreesC).

The enantiomers of asymmetric nitrogen compound 1 have been resolved; a chiral formal meso-form of diaziridine 2 has been obtained; a population of 1,2-cis-form 6a in solution has been found; and the crystal structures of 3–6 have been studied.

Prochiral substrates (alkyl aryl ketones, cyclopropyl methyl ketone, 1-indanone, 1-tetralone, ethyl 2-oxo-4-phenylbutyrate, and N -(diphenylphosphinyl)acetophenoneimine) were subjected to asymmetric reduction with aluminum hydride reagents, which were prepared by modifications of NaAlH 4 or AlH 3 with chiral α,α,α",α"-tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOL). The effects of the nature of the substituents in TADDOL, the structure of the prochiral substrate, and the reaction conditions on the stereochemistry of reduction were investigated. The highest enantioselectivity (70—90% ee ) was achieved upon reduction of alkyl aryl ketones and N -(diphenylphosphinyl)acetophenoneimine with NaAl(TADDOLate)H 2 in THF or diglyme at a temperature from –70 to –20 °C. The mechanism of asymmetric induction in the reduction reactions of ketones with aluminum hydride reagents is discussed. The stereochemical results of reduction were explained by comparing three-dimensional models of the most probable transition states.

Asymmetric reduction of ketones with hydride complexes, which were prepared by in situ modification of NaAlH4, with various chiral amino alcohols or diamines, was studied. The highest enantioselectivity (up to 93% ee) was achieved using 2-(hydroxydiphenylmethyl)pyrrolidine as a chiral inducing agent.

Rhodium and iridium complexes of Schiff's bases derived from (1 R ,2 R )- and (1 S ,2 S )-diaminocyclohexane catalyze asymmetric transfer hydrogenation of alkyl aryl ketones in Pr i OH at room temperature to give chiral secondary alcohols (up to 65% ee ).

Pure enantiomers of chromium tricarbonyl complexes of α- and β-monosubstuted naphthalenes RC10H7Cr(CO)3 (R=Cl, Me, SiMe3, SnMe3) were separated as pure enantiomers by chiral phase HPLC on a Chiracel OD column. Inter-ring haptotropic rearrangements (IRHRs) (process in which metal shifts between substituted and non-substituted rings) of pure enantiomers were investigated in different solvents in the presence or absence of some solvating additives. It was shown that IRHR proceeds at 85°C in noncoordinative and noncomplexing solvents such as hexafluorobenzene or decane through an intermolecular mechanism without racemization. In aromatic toluene, which can bind with the organometallic group, it proceeds through a partially intramolecular mechanism, leading to considerable racemization (ca. 20%) of the complexes. In the presence of solvating additives (THF, dibutyl ether), almost complete racemization (>90%) was observed.

The catalytic activity and the enantioselectivity manifested by cationic chiral binaphthylbisphosphine ruthenium complexes in asymmetric hydrogenation of β-keto esters were studied. The effects of the nature of the solvent, the reaction temperature, the pressure, addition of acids, and the reagent ratio on the yield and the degree of enantiomeric enrichment of the reaction products were examined. For hydrogenation of ethyl 4-chloroacetoacetate to form (R)- or (S)-enantiomers of ethyl 4-chloro-3-hydroxybutyrate, conditions were found which allow one to quantitatively prepare this valuable synthon with high enantiomeric purity (97–99%) at a low concentration of the catalyst (the ratio substrate: Ru=10000).