The bowl-shaped supramolecular scaffold cyclotriveratrylene (CTV) has been studied extensively because of its ability to function as a host in host-guest chemistry for C60 as well as for a number of other small molecules, and its use in construction of cryptands. Our research has focused on apex-modified CTV derivatives and reactivity and their molecular dynamics.
The azacyclophane “N3-CTV” is an apex-modified analog of CTV including three aniline nitrogens comprising the macrocyclic 9-membered ring. We discovered a remarkable oxidative rearrangement to a stable cation radical, and we have also observed the fascinating di-iron complex (left).
Synthesis of N3-CTV
The synthesis of N3-CTV proceeds via sequential Buchwald-Hartwig coupling reactions.