"The Sulfur Dance" Around Arenes and Heteroarenes - the Reversible Nature of Nucleophilic Aromatic Substitutions.
Fiche publication
Date publication
janvier 2024
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
Auteurs
Membres identifiés du Cancéropôle Est :
Pr LEHN Jean-Marie
Tous les auteurs :
Gahlot S, Schmitt JL, Chevalier A, Villa M, Roy M, Ceroni P, Lehn JM, Gingras M
Lien Pubmed
Résumé
We disclose the features of a category of reversible nucleophilic aromatic substitutions in view of their significance and generality in dynamic aromatic chemistry. Exchange of sulfur components surrounding arenes and heteroarenes may occur at 25°C, in a process that one may call a "sulfur dance". These SNAr systems present their own features, apart from common reversible reactions utilized in dynamic chemistry (DCC). By varying conditions, covalent dynamics may operate to provide libraries of thiaarenes with some selectivity, or conversion of a hexa(thio)benzene asterisk into another one. The reversible nature of SNAr is confirmed by three methods: a convergence of the products distribution in reversible SNAr systems, a related product redistribution between two per(thio)benzenes by using a thiolate promoter, and from kinetic/thermodynamic data. A four-component dynamic covalent system further illustrates the thermodynamically-driven formation of a thiacalix[2]arene[2]pyrimidine by sulfur component exchanges. This work stimulates the implementation of reversible SNAr in aromatic chemistry and in DCC.
Mots clés
Sulfur * SNAr * ThiaArenes * Reversible reactions * Macrocycles * Aromatic chemistry
Référence
Chemistry. 2024 01 30;:e202400231