Formation mechanism and conformational structure of 2,3,4-trimethyl-1,5-di(thiophen-2-yl)pentane-1,5-dione: quantum chemical study
| Autor: | E. Yu. Shmidt, E. Yu. Larionova, Vladimir B. Kobychev, Nadezhda M. Vitkovskaya, Boris A. Trofimov |
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| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Ketone Double bond 010405 organic chemistry General Chemistry 010402 general chemistry 01 natural sciences Polarizable continuum model Medicinal chemistry 0104 chemical sciences Pentane chemistry.chemical_compound chemistry Acetylene Computational chemistry Solvent effects Carbanion Octane |
| Zdroj: | Russian Chemical Bulletin. 65:394-400 |
| ISSN: | 1573-9171 1066-5285 |
| DOI: | 10.1007/s11172-016-1311-5 |
| Popis: | The mechanism of formation of 1,5-diketone, a key intermediate in the stereoselective assembly of 2,3,4-trimethyl-7-methylidene-1,5-di(thiophen-2-yl)-6,8-dioxabicyclo[3.2.1]octane, and the conformational structures of the reagents and products were studied by quantum chemical calculations at the MP2/6-311++G**//B3LYP/6-31G* level of theory with solvent effects treated within the polarizable continuum model. The activation barrier for the addition of the 1-oxo-1-(thiophen-2-yl)propan-2-ide ion (1), which is generated from 1-(thiophen-2-yl)propan-1-one, to acetylene is 15.2 kcal mol–1. The reaction affords β,γ-unsaturated ketone. The subsequent addition of carbanion 1 to the C=C double bond of the resulting β,γ-unsaturated ketons yields 1,5-diketone and occurs with insignificant (less than 1 kcal mol–1) activation barrier. |
| Databáze: | OpenAIRE |
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