Alkyland arylketone reactions with phenylacetylene promoted by KOH—DMSO superbase: a quantum chemical study

Autor:	Vladimir B. Kobychev, Vladimir B. Orel, E. Yu. Schmidt, Nadezhda M. Vitkovskaya, Boris A. Trofimov
Rok vydání:	2015
Předmět:	chemistry.chemical_classification Quantum chemical chemistry.chemical_compound Reaction mechanism Ketone Phenylacetylene chemistry Superbase Reactivity (chemistry) General Chemistry Photochemistry Isomerization Carbanion
Zdroj:	Russian Chemical Bulletin. 64:518-524
ISSN:	1573-9171 1066-5285
DOI:	10.1007/s11172-015-0895-5
Popis:	Mechanisms of ethynylation and vinylation of ketones with phenylacetylene in the presence of KOH•5DMSO superbase were studied using the MP2/6-311++G**//B3LYP/6-31+G* approach. The thermal effects and activation barriers to individual reaction stages were evaluated. It was shown that stereoscpecificity of ketone vinylation with PhC≡CH is due to the possibility of isomerization of both carbanion intermediates and enolate anions originating from the final β,γ-unsaturated ketones. The calculated activation energies of the vinylation of substituted ketones are in good agreement with the experimentally observed differences in their reactivity with respect to the addition of phenylacetylene.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::4c03657d8d759ed9bd8dc3f4709930fe https://doi.org/10.1007/s11172-015-0895-5 Zobrazit plný text záznamu Full text from SpringerLink