Post-Synthetic Macrocyclization of Rotaxane Building Blocks

Abstract

Although not often encountered, cyclic interlocked molecules are appealing molecular targets because of their restrained tridimensional structure which is related to both the cyclic and interlocked shapes. Interlocked molecules such as rotaxane building blocks may be good candidates for post-synthetic intramolecular cyclization if the preservation of the mechanical bond ensures the interlocked architecture throughout the reaction. This is obviously the case if the modification does not involve the cleavage of either the macrocycle's main chain or the encircled part of the axle. However, among the post-synthetic reactions, the chemical linkage between two reactive sites belonging to embedded elements of rotaxanes still consists of an underexploited route to interlocked cyclic molecules. This Review lists the rare examples of macrocyclization through chemical connection between reactive sites belonging to a surrounding macrocycle and/or an encircled axle of interlocked rotaxanes.

Keywords: catenanes; cyclization; mechanical bonds; rotaxanes; supramolecular chemistry.