How the Nature of an Alpha-Nucleophile Determines a Brønsted Type-Plot and Its Reaction Pathways. An Experimental Study

Paola R Campodónico; Ricardo A Tapia; Cristian Suárez-Rozas

doi:10.3389/fchem.2021.740161

How the Nature of an Alpha-Nucleophile Determines a Brønsted Type-Plot and Its Reaction Pathways. An Experimental Study

Front Chem. 2022 Feb 2:9:740161. doi: 10.3389/fchem.2021.740161. eCollection 2021.

Authors

Paola R Campodónico¹, Ricardo A Tapia², Cristian Suárez-Rozas¹

Affiliations

¹ Centro de Química Médica, Instituto de Ciencias e Innovación en Medicina, Clínica Alemana Universidad del Desarrollo, Santiago, Chile.
² Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, Chile.

Abstract

The reactions between 2-chloro-5-nitro pyrimidine with a serie of α-nucleophile derivatives were kinetically evaluated. The kinetic study was carried out in aqueous media and the data shown an unusual split on the Brønsted type-plot, opening a controversial discussion based on reactivities and possible reaction pathways. These split Brønsted type-plots are discussed over the hypothetical transition state (TS) structures associated to concerted or stepwise mechanisms with emphasis on hydrogen bond interactions between electrophile/nucleophile pair able to determine the reactivities and the plausible reaction routes.

Keywords: SNAr reactions; brønsted type-plots; hydrogen bond interaction; mechanisms; reactivity.