Abstract: The synthesis and chemistry of polycyclic cage compounds have attracted considerable attention in recent years.¹ The vast majority of the work reported in this area has dealt with caybocyclic cage compounds. On the other hand, the synthesis and chemistry of heterocyclic cage compounds have received less attention. Recently, we have accomplished the synthesis of a series of oxa-cage compounds and performed the chemical transformations of these oxa-cage compounds.² As part of a program that involves the synthesis,chemistry and applications of heterocyclic cage compounds we report here the synthesis of heterocyclic cage compounds 1-12. We also wish to report the applications of compounds 7-12 on the π-facial selectivities. Studies on the cation-binding properties of compounds 1 and 2 and other oxa-cages are undertaken.