"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

https://www.ncbi.nlm.nih.gov/pubmed/38289151

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.