Abstract:
The kinetic (free activation energies) and thermodynamic factors, which ensure mild conditions for the ethynylation of imines with acetylenes, have been established by quantum chemical calculations using B2PLYP/6-311+G**//B3LYP/6-31+G*. According to the calculations, the alternative route of superbase catalyzed C-vinylation requires harsher reaction conditions as compared to the ethynylation one.
Citation:
V. B. Orel, N. M. Vitkovskaya, D. Z. Absalyamov, E. Yu. Schmidt, B. A. Trofimov, “Quantum chemical comparison of ethynylation and C-vinylation routes in superbase catalyzed reaction of acetylenes with imines”, Mendeleev Commun., 29:6 (2019), 622–624
Linking options:
https://www.mathnet.ru/eng/mendc1608
https://www.mathnet.ru/eng/mendc/v29/i6/p622
This publication is cited in the following 5 articles:
E. Yu. Schmidt, B. A. Trofimov, “Acetylene in Organic Synthesis. From the Chaos of Small Molecules to Highly Organized Structures. A Review”, Dokl Chem, 505:1 (2022), 127
D Z Absalyamov, N M Vitkovskaya, “Quantum-chemical description of interactions in the PhNH2/HCCH system in a superbasic medium”, J. Phys.: Conf. Ser., 1847:1 (2021), 012049
Vladimir B. Orel, Anastasia A. Manzhueva, “Thermodynamics and isomerism of products and intermediates of a one-pot superbase-promoted assembly of tetracyclic frontalin derivatives: A quantum chemical study”, Journal of Molecular Structure, 1215 (2020), 128290
Nadezhda M. Vitkovskaya, Vladimir B. Orel, Damir Z. Absalyamov, Boris A. Trofimov, “Self-Assembly of N-Phenyl-2,5-dimethylpyrrole from Acetylene and Aniline in KOH/DMSO and KOBut/DMSO Superbase Systems: A Quantum-Chemical Insight”, J. Org. Chem., 85:16 (2020), 10617
L. A. Oparina, N. A. Kolyvanov, N. K. Gusarova, B. A. Trofimov, “Chemoselective vinylation of aminophenols with acetylene catalyzed by sodium aminophenolates in aqueous DMSO”, Mendeleev Commun., 30:6 (2020), 788–790
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