6533b851fe1ef96bd12a8bd6

RESEARCH PRODUCT

Understanding the domino reactions of alkyne-tethered N-tosylhydrazones yielding fused polycyclic pyrazoles. An MEDT study

Mar Ríos-gutiérrezFatemeh GhodsiSaeedreza EmamianLuis R. DomingoSayyed Mostafa Habibi-khorassaniMehdi Shahraki

subject

chemistry.chemical_classificationIntramolecular reaction010405 organic chemistryChemistryOrganic ChemistryAlkyneBond formation010402 general chemistry01 natural sciencesBiochemistryCycloadditionDomino0104 chemical sciencesIonGibbs free energysymbols.namesakeComputational chemistryIntramolecular forceDrug Discoverysymbols

description

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.

yearjournalcountryeditionlanguage
2019-05-01Tetrahedron
https://doi.org/10.1016/j.tet.2019.03.059