Upper-rim monofunctionalisation in the synthesis of triazole- and disulfide-linked multicalix[4]- and -[6]arenes

Covalently linked multiple calixarenes are valued in supramolecular chemistry. We report an easy and versatile synthetic route to covalently linked double and triple calix[4]arene and calix[6]arenes by a novel DMF‐controlled selective alkylation of a convenient and readily available upper‐rim dimethylaminomethyl‐substituted tetrahydroxy calix[4]arene and ‐[6]arenes. Synthetic routes to upper‐rim functionalised redox active disulfide‐linked double‐, tetra‐ and peptidohybrid‐calixarenes employing either redox chemistry (CH₂SH) or thiolates (CH₂S^–) are also opened up from the same key starting material.