Computational studies on reactions conducted in a (nano)confined space

The behavior of molecules confined to small spaces is fascinating and lies at the heart of biological enzymatic processes. The approach to confinement is through reversible encapsulation of small molecules in synthetic supramolecular containers, which leads to amplified reactivities in chemical reactions, stabilization of otherwise reactive species, and limitation in motions that create new stereochemical arrangements with stereochemical outcomes different from those explored in a non-nanoconfined environment. The isolation of molecules from solvent makes for manageable computations and has stimulated theorists to examine reaction details in the nanoconfined space. Transition states for reactions and rearrangements can be calculated, the effects of (de)solvation can be evaluated, and the properties of the containers can be compared with experimental observations. Finally, several potential applications will be outlined.