Catenation of calixarene annulus.

Through-the-annulus-catenated calixarenes have been obtained, for the first time, by exploiting the "superweak anion" approach that allows the threading of the calix cavity with functionalized dialkylammonium axles. In addition, the first example of a stereoprogrammed synthesis of a catenane orientational isomer (an oriented calix[2]catenane) has been obtained, after macrocyclization, by using a directional alkylbenzylammonium axle.