Organic Chemistry in Russian Universities: Achievements of recent years

Журнал органической химии, Journal Year: 2024, Volume and Issue: 60(2-3)

Published: Dec. 27, 2024

Language: Английский

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Solvent-modulated Binding Selectivity of Reaction Substrates to Onium-based Sigma-Hole Donors

Published: Jan. 2, 2023

The combination of experimental data and results DFT calculations indicates that the catalytic activity chalconium halonium salts serving as sigma-hole donating organocatalysts cannot be clearly estimated via analysis electrostatic potential on catalysts’ sigma-holes values catalyst•••TS intermolecular interactions, such polarization effects, charge transfer, or covalency bonding. Moreover, real effect might not correlate well with Gibbs free energy activation reactions, because solvation effects other competitive binding processes play at least an equal even more important role in catalysis. It was shown present work can either lead to increase equilibrium concentration reactive catalyst•••electrophile associates, thus accelerating reaction, brings favorable generation catalyst•••nucleophile species resulting suppression organocatalyst.

Language: Английский

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Cooperative Catalysis Involving Hydrogen and Halogen Bond Donors: A Computational Study on the Thiourea–Iodonium System

Published: April 3, 2023

A computational analysis of possible routes cooperative catalysis involving hydrogen bond (HB) and halogen (XB) donating organocatalysts has been carried out. Previously suggested route including electrophilic activation HB donor by XB was ruled out but a path double reaction electrophile its simultaneous association with the species confirmed DFT calculations.

Language: Английский

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Solvent-modulated Binding Selectivity of Reaction Substrates to Onium-based Sigma-Hole Donors

Published: Dec. 20, 2022

Combination of experimental data and results DFT calculations indicates that the catalytic activity chalconium halonium salts served as sigma-hole donating organocatalysts cannot be clearly estimated via analysis electrostatic potential on catalysts’ sigma-holes values catalyst•••TS intermolecular interactions, such polarization effects, charge transfer, or covalency bonding. Moreover, real effect might not correlate well with Gibbs free energies activation reactions, because solvation effects other competitive binding processes play at least same even more important role in catalysis. It was showed present work, either can lead to increase equilibrium concentration reactive catalyst•••electrophile associates thus accelerating reaction brings favorable generation catalyst•••nucleophile species resulting suppression organocatalyst.

Language: Английский

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Theoretical Studies and Computer Modeling of Supramolecular Chemical Systems: Structure, Properties and Reactivity

The 17th International Electronic Conference on Synthetic Organic Chemistry, Journal Year: 2022, Volume and Issue: unknown, P. 88 - 88

Published: Nov. 18, 2022

The results of my research in the fields theoretical studies and computer modeling supramolecular chemical systems were presented. main attention was focused on following topics: cycloaddition nucleophilic addition reactions involving substrates with multiple CC CN bonds, their mechanisms, driving forces, kinetics thermodynamics; consideration catalysis hydrocarbons oxidation processes conversion to alcohols, ethers, aldehydes, ketones carboxylic acids; investigations various unusual types non-covalent interactions (from quite trivial hydrogen bonds more exotic σ-hole, π-hole metallophilic interactions) organic, organometallic coordination compounds. Some fundamental issues also discussed (e.g., structure properties compounds associates; conformational transitions rotation barriers functional groups; nature bonds; orbital charge factors; photophysical properties).

Language: Английский

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