A Theoretical Study of the Relationship between the Electrophilicity ω Index and Hammett Constant σp in [3+2] Cycloaddition Reactions of Aryl Azide/Alkyne Derivatives
Hicham Ben El Ayouchia,
Hafid Anane,
Moulay Lahcen El Idrissi Moubtassim,
Luis R. Domingo,
Miguel Julve,
Salah-Eddine Stiriba
Affiliations
Hicham Ben El Ayouchia
Laboratoire de Chimie Analytique et Moléculaire, Faculté Polydisciplinaire de Safi, Université Cadi Ayyad, Safi 46010, Morocco
Hafid Anane
Laboratoire de Chimie Analytique et Moléculaire, Faculté Polydisciplinaire de Safi, Université Cadi Ayyad, Safi 46010, Morocco
Moulay Lahcen El Idrissi Moubtassim
Laboratoire de Chimie Analytique et Moléculaire, Faculté Polydisciplinaire de Safi, Université Cadi Ayyad, Safi 46010, Morocco
Luis R. Domingo
Departamento de Química Orgánica, Universidad de Valencia, Avda. Dr. Moliner 50, Burjassot 46100, Valencia, Spain
Miguel Julve
Instituto de Ciencia Molecular/ICMol, Universidad de Valencia, C/Catedrático José Beltrán No. 2, Paterna 46980, Valencia, Spain
Salah-Eddine Stiriba
Laboratoire de Chimie Analytique et Moléculaire, Faculté Polydisciplinaire de Safi, Université Cadi Ayyad, Safi 46010, Morocco
The relationship between the electrophilicity ω index and the Hammett constant σp has been studied for the [2+3] cycloaddition reactions of a series of para-substituted phenyl azides towards para-substituted phenyl alkynes. The electrophilicity ω index—a reactivity density functional theory (DFT) descriptor evaluated at the ground state of the molecules—shows a good linear relationship with the Hammett substituent constants σp. The theoretical scale of reactivity correctly explains the electrophilic activation/deactivation effects promoted by electron-withdrawing and electron-releasing substituents in both azide and alkyne components.
