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Updated: Jan 10, 2026

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
Acridane[4]Arenes: Scope of the Macro-Tetramerization, Derivatization Options, and Water-Soluble Derivatives
Vera Höft1, Jonathan Pfeuffer-Rooschüz1, Ricard López-Coll1
1Department of Chemistry, University of Basel, Basel, Switzerland.
Abstract:
Macrocycles are essential scaffolds in supramolecular chemistry, offering versatile platforms for functionalization. Here, we report the optimization, expanded scope, and comprehensive derivatization strategies for acridane[4]arenes (A4A), a large macrocyclic platform featuring a conformationally restricted bowl shape analogous to resorcin[4]arene. The scope of the macrocyclization was expanded with four distinct 'feet' substituents at the lower rim. Strategies for selective functionalization at the upper rim were developed, including N-Boc protection at each acridane subunit. This modification induced self-assembly into a dimeric cage in apolar solvents, which form stable host-guest complexes with tetrabutylammonium salts. Further functionalization of the acridane nitrogen via Buchwald-Hartwig cross-coupling allowed installation of aromatic groups bearing diverse functional handles. Finally, water-soluble A4A derivatives were achieved by introducing charged ionic 'feet' substituents, such as 1-methylimidazolium. These results establish A4As as a highly modular macrocyclic platform with broad potential for supramolecular applications.
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