Fiche publication
Date publication
avril 2022
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
Auteurs
Membres identifiés du Cancéropôle Est :
Dr CHAMBRON Jean-Claude
Tous les auteurs :
Schleife F, Bonnot C, Chambron JC, Börner M, Kersting B
Lien Pubmed
Résumé
The syntheses and properties of expanded 4-tert-butyl-mercaptocalix[4]arenes, in which the methylene linkers are replaced by -CH NRCH - or -CH NRCH - and -CH NRCH CH CH NRCH - units, are described. The new macrocycles were obtained in a step-wise manner, utilizing fully protected, i. e. S-alkylated, derivatives of the oxidation-sensitive thiophenols in the cyclisation steps. Reductive cleavage of the macrobicyclic or macrotricyclic intermediates (6, 7, 11) afforded the free thiophenols (H 8, H 9, and H 12) in preparative yields as their hydrochloride salts. The protected proligands can exist in two conformations, resembling the "cone" and "1,3-alternate" conformations found for the parent calix[4]arenes. The free macrocycles do not show conformational isomerism, but are readily oxidized forming intramolecular disulfide linkages. Preliminary complexation experiments show that these expanded mercaptocalixarenes can serve as supporting ligands for tetranuclear thiolato clusters.
Mots clés
X-ray crystallography, coordination chemistry, expanded mercaptocalix[4]arenes, synthesis
Référence
Chemistry. 2022 04 12;28(21):e202104255
