Supramolecular Catalysis of a Unimolecular Transformation: Aza‐Cope Rearrangement within a Self‐Assembled Host
Catalytic containers: A supramolecular metal–ligand assembly [M4L6] is utilized as a catalytic host for the unimolecular carbon–carbon bond-forming rearrangement of enammonium cations (see scheme). The restricted reaction space of the supramolecular structure forces the substrate to adopt a reactive conformation upon binding to the interior. The assembly achieves up to 850-fold rate acceleration of the rearrangement.