Understanding the domino reactions of alkyne-tethered N-tosylhydrazones yielding fused polycyclic pyrazoles. An MEDT study
| Autor: | Mar Ríos-Gutiérrez, Fatemeh Ghodsi, Saeedreza Emamian, Luis R. Domingo, Sayyed Mostafa Habibi-Khorassani, Mehdi Shahraki |
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| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Intramolecular reaction 010405 organic chemistry Chemistry Organic Chemistry Alkyne Bond formation 010402 general chemistry 01 natural sciences Biochemistry Cycloaddition Domino 0104 chemical sciences Ion Gibbs free energy symbols.namesake Computational chemistry Intramolecular force Drug Discovery symbols |
| Zdroj: | Tetrahedron. 75:2807-2816 |
| ISSN: | 0040-4020 |
| Popis: | The domino reactions of alkyne-tethered N-mesylhydrazones yielding fused polycyclic pyrazoles have been studied within the Molecular Electron Density Theory (MEDT). Analysis of the Gibbs free energies indicates that the more favourable reactive path is the one in which the elimination of mesylate anion takes place before the intramolecular [3 + 2] cycloaddition (IM32CA) reaction, which corresponds with the rate-determining step of these domino processes. ELF topological analysis of the bond formation along the IM32CA reaction indicates that in spite of the high activation energy associated to this intramolecular reaction, it shows a pmr-type mechanism characterised by the presence of a pseudoradical carbon at the phenyldiazomethane framework. |
| Databáze: | OpenAIRE |
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