In the confined space of supramolecular systems, the substrate can be forced into a reactive conformation and labile intermediates may be stabilized while isolated from the bulk solution. In this highlight, unusual processes mediated by supramolecular hosts are described. These include unfavourable conformational equilibria, unusual product selectivities in bond and ring-chain isomerizations, accelerated rearrangement reactions through labile intermediates, and encapsulated oxidations. In the host, controlled or altered isomerization of the guests can occur via hydrophobic, photochemical and thermal interventions. The inner spaces of the hosts resemble enzyme cavities that stabilize labile intermediates not accessible in the bulk solvent. The effects of confinement and the binding forces involved are discussed and further applications are suggested.