Mechanically interlocked molecules have a long and rich history as ligands thanks to the key role coordination chemistry has played in the development of high yielding passive template syntheses of rotaxanes and catenanes. In this Feature Article, we highlight the effect of the mechanical bond on the properties of metal ions bound within the sterically hindered environment of the macrocycle cavity, and discuss the emerging applications of interlocked ligands in catalysis, sensing and supramolecular materials.

Chiral interlocked molecules in which the mechanical bond provides the sole stereogenic unit are typically produced with no control over the mechanical stereochemistry. Here we report a stereoselective approach to mechanically planar chiral rotaxanes in up to 98:2 d.r. using a readily available α‐amino acid‐derived azide. Symmetrization of the covalent stereocenter yields a rotaxane in which the mechanical bond provides the only stereogenic element.

A rotaxane-based Au catalyst was developed and the effect of the mechanical bond on its behavior was studied. Unlike the non-interlocked thread, the rotaxane requires a catalytically innocent cofactor, the identity of which significantly influences both the yield and diastereoselectivity of the reaction. Under optimized conditions, AuI (the catalyst), AgI (to abstract the Cl− ligand), and CuI (the cofactor) combine to produce a catalyst with excellent activity and selectivity.

We present a simple approach to bipyridine macrocycles in remarkable yields (typically >65%) and demonstrate their application in efficient rotaxane synthesis.

A gold-catalyzed regioselective tandem cyclization of N-propynylbutynamide via Csp(3)-H functionalization has been described, providing a distinctive methodology for the architecture of cyclopentapyridinones as well as spirocyclopentapyridinones.