A5032588871- Synthesis and Characterization of Pyrroles
- Fluorine in Organic Chemistry
- Advanced Chemical Physics Studies
- Chemical Reaction Mechanisms
- Organic Chemistry Cycloaddition Reactions
- Molecular Spectroscopy and Structure
- Inorganic and Organometallic Chemistry
- Chemical Thermodynamics and Molecular Structure
- Sulfur-Based Synthesis Techniques
- Porphyrin and Phthalocyanine Chemistry
- Catalytic C–H Functionalization Methods
- Crystallography and molecular interactions
- Free Radicals and Antioxidants
- Click Chemistry and Applications
- Ionic liquids properties and applications
- Chemical Reactions and Mechanisms
- Oxidative Organic Chemistry Reactions
- Crystallization and Solubility Studies
- Molecular Junctions and Nanostructures
- Synthesis and Reactions of Organic Compounds
- Catalysis and Oxidation Reactions
- Catalysis for Biomass Conversion
- Cyclopropane Reaction Mechanisms
- Advanced NMR Techniques and Applications
- Inorganic Fluorides and Related Compounds
Irkutsk State University
2014-2025
A.E. Favorsky Irkutsk Institute of Chemistry
1990-2021
American Petroleum Institute
1987
The complete valence shell photoelectron spectra of cytosine, thymine and adenine have been investigated experimentally theoretically. Vertical ionization energies spectral intensities evaluated using the many-body Green's function method, thereby enabling theoretical to be derived. In influence tautomers rotational conformers has investigated. calculated display a satisfactory agreement with experimental data this allowed most bands assigned. Photoelectron asymmetry parameters determined...
Abstract Possible mechanisms of cyclodimerization benzoylethynyl pyrrole to give 2,2′‐(dipyrrolo[1,2‐a:1′,2′‐d]pyrazine‐5,10‐diylidene)bis(1‐phenylethanone) have been investigated by using a DFT B2PLYP‐D3/6–311+G**//B3LYP‐D3/6–31+G*+PCM/MeCN approach. This study shows that the induced 1‐methylimidazole, and observed in presence strong bases (NaOH or KOH) occur different mechanisms. The reaction pathway involving which starts with formation zwitterionic adduct, was compared cyclization as...
A CBS-Q//B3 based study has been carried out to elucidate the mechanism of KOH/DMSO superbase catalyzed ketones nucleophilic addition alkyl propargyl and allenyl ethers yielding, along with (Z)-monoadducts, up 26% unexpected (E)-diadducts. The impact different substrates (alkynes versus allenes) on reaction discussed in detail. Along model acetone propyne allene, acetophenone methyl is considered. limiting stage starting ketone carbanion systems occurs activation energies typical for...
Abstract The mechanisms of fundamental base‐promoted acetylene reactions, namely, nucleophilic addition to the triple C ≡ bond (vinylation) and acetylenic carbanion a carbonyl group (ethynylation), are addressed using three models different complexity—pentasolvate, monosolvate, anionic—which describe catalytic superbasic systems MOH(OBu t )/DMSO (suspensions alkali hydroxides or tert ‐butoxides in dimethyl sulfoxide). above reactions sequential transformations reagents arranged by center...
A rapidly developing approach adding new dimensions to acetylene chemistry relying on employment of high basicity media such as alkali metal hydroxide suspensions in dimethyl sulfoxide (DMSO) has been, for the first time, investigated theoretically using ab initio models. Extending our recently introduced model superbase catalysis with a nondissociated KOH (or NaOH) participation, we present here superbasic reaction center solvation shell explicitly included. The hydroxides DMSO solution...
Abstract The reaction mechanism of methanol vinylation with acetylene involving a nondissociated KOH molecule was studied using the MP2/6‐311++G**//HF/6‐31+G* approach DMSO explicitly included into system. whole conversion cycle including active nucleophile generation, bonding latter to moiety yielding an intermediate carbanion, final methyl vinyl ether formation, and potassium hydroxide regeneration could be realized in coordination shell KOH. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011
Abstract The mechanisms of reactions between electron‐deficient acetylenes, specifically acylpyrrolylacetylenes, and 1‐pyrrolines were examined using a DFT B2PLYP‐D3/6‐311++G**//B3LYP/6‐31+G* approach. study was focused on the interaction 1‐phenyl‐3‐(1 H ‐pyrrol‐2‐yl) prop‐2‐yn‐1‐one with 5‐methyl‐3,4‐dihydro‐2 ‐pyrrole, aimed at clearer understanding reaction progress. pathway for synthesis dipyrroloimidazole derivative comprising three five‐membered nitrogen‐containing heterocycles is...
Transition-metal-free C-vinylation of acetone with phenylacetylene catalyzed by superbases MOH/DMSO and tBuOM/DMSO (M = Na, K) has been theoretically evaluated in the B3LYP/6-311++G**//B3LYP/6-31+G* approach to rationalize similarities differences activity above catalytic systems. The close solvate surroundings sodium potassium tert-butoxides have studied. Formation tBuOM·nDMSO complexes their structure thermodynamic stability are discussed comparison similar alkali-metal hydroxides...
Abstract The mechanism of base‐catalyzed nucleophilic addition methanol to acetylene triple bond (vinylation) in dimethyl sulfoxide (DMSO) and solution was studied using the MP2/6‐311++G**//B3LYP/6‐31G* calculations with solvent effects included via continuum model. proton abstraction from by nondissociated alkali DMSO surrounding media form metal methoxides CH 3 OM ( M = Li, Na, K) found occur a negligible activation barrier. reasons for facilitation alcohol vinylation medium are discussed...
Abstract Most of the strategies for synthesis 6,8‐dioxabicyclo[3.2.1]octanes (BCO) and cyclopentenols (CP), which show high biological pharmaceutical activity, are multistage and/or require hardly accessible starting materials catalysts. The general method BCO CP preparation in a single preparative stage from two simple reagents, ketones acetylene, under action an available super‐basic catalytic system KOH/DMSO becomes promising development approaches to design these classes biologically...
Abstract The ability of protocols based on the B2PLYPD/6-311+G**//B3LYP/6-31+G* method with various schemes for accounting nonspecific solvation to reproduce C-H, N-H, O-H and S-H acidity in a dimethyl sulfoxide medium is considered. For selected set 20 compounds, typical reagents reactions superbasic media, IEFPCM scheme UFF cavity α = 1.35 multiplier yields better results than popular SMD model.