Chemistry in Restricted Spaces: Select Photodimerizations in Cages, Cavities, and Capsules

Carrying out chemical transformations under environmentally sustainable conditions has become one of the important current goals of chemistry. In this context, conducting reactions under solvent-free corditions (crystals, zeolites, clay, etc.) and in water has attracted considerable attention. Since most molecules either do not crystallize and or do not dissolve in water, the two approaches are complimentary. To make molecules solubilize in water one needs to employ water-soluble hosts such as micelles, cavitands, and capsules. To achieve selectivity, one should provide a confined environment within which the motions of reactant molecules are restricted to that in free solution. The confined space in which the reaction takes place independent of the host environment could be defined in terms of the reaction cavity originally presented by Cohen and Schmidt. In this mini-review, examples of photodimerization of olefins carried out in cavitands such as cucurbiturils, cyclodextrins, calixarenes, and octa acid are presented. Results are discussed in terms of the reaction cavity concept, which is applicable to reactions in both solids and water.