Meisenheimer complexes as hidden intermediates in the aza-SNAr mechanism

Ormazabal-Toledo, Rodrigo; Richter, Sebastian; Robles-Navarro, Andres; Maulen, Boris; Matute, Ricardo A.; Gallardo-Fuentes, Sebastian

Abstract

In this work we report a computational study about the aza-SNAr mechanism in fluorine- and chlorine-containing azines with the aim to unravel the physical factors that determine the reactivity patterns in these heterocycles towards propylamine. The nature of the reaction intermediate was analyzed in terms of its electronic structure based on a topological analysis framework in some non-stationary points along the reaction coordinate. The mechanistic dichotomy of a concerted or a stepwise pathway is interpreted in terms of the qualitative Diabatic Model of Intermediate Stabilization (DMIS) approach, providing a general mechanistic picture for the SNAr process involving both activated benzenes and nitrogen-containing heterocycles. With the information collected, a unified vision of the Meisenheimer complexes as transition state, hidden intermediate or real intermediate was proposed.

Más información

Título según WOS: Meisenheimer complexes as hidden intermediates in the aza-SNAr mechanism
Título de la Revista: ORGANIC AND BIOMOLECULAR CHEMISTRY
Volumen: 18
Número: 22
Editorial: The Royal Society of Chemistry
Fecha de publicación: 2020
Página de inicio: 4238
Página final: 4247
DOI:

10.1039/D0OB00600A

Notas: ISI