Thioderivatives of Resorcin[4]arene and Pyrogallol[4]arene: Are Thiols Tolerated in the Self-Assembly Process?

Three novel thiol bearing resorcin[4]arene and pyrogallol[4]arene derivatives were synthesized. Their properties were studied with regards to self-assembly, disulfide chemistry, and Brønsted acid catalysis. This work demonstrates that (1) one aromatic thiol on the resorcin[4]arene framework is tolerated in the self-assembly process to a hexameric hydrogen bond-based capsule, (2) thio-derivatized resorcin[4]arene analogs can be covalently linked through disulfides, and (3) the increased acidity of aromatic thio-substituent is not sufficient to replace HCl as cocatalyst for capsule catalyzed terpene cyclizations.