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Understanding the domino reactions of alkyne-tethered N-tosylhydrazones yielding fused polycyclic pyrazoles. An MEDT study |
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| Authors: | Fatemeh Ghodsi Sayyed Mostafa Habibi-Khorassani Mehdi Shahraki Saeedreza Emamian Mar Ríos-Gutiérrez Luis R. Domingo |
| Affiliation: | 1. Department of Chemistry, University of Sistan and Baluchestan, Zahedan, Iran;2. Chemistry Department, Shahrood Branch, Islamic Azad University, Shahrood, Iran;3. Department of Organic Chemistry, University of Valencia, Dr Moliner 50, 46100 Burjassot, Valencia, Spain |
| Abstract: | 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. |
| Keywords: | Pyrazoles Domino reactions Intramolecular [3+2] cycloadditions Molecular electron density theory Molecular mechanisms |
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