Co-host: The Chemical Society of Japan, The Society of Synthetic Organic Chemistry, Japan (Cooperation)
Cavity-directed chemical transformations represent one of the most important features of three-dimentional hosts, but yet have been less explored in previous synthetic receptors. We are developing such functions with the large cavity of the self-assembled cages, particularly an M6L4-type cage complex shown in the Scheme. The photodimerization of olefins in this cage is featured, for example, by remarkable rate enhancement (>102 times), perfect regio- and stereo-selection, and high pairwise selection (when two different olefins are used) giving only a cross [2+2] adduct. Another intriguing property of the cavity is the stabilization of labile molecules by encapsulation. We succeeded in trapping a labile molecule by preparing it in situ from small components coming through small portals of the cage. Cavity-sensitized photochemical reaction as well as endohedral clusterization of water molecules in the cavity will be also discussed.
