Hemicryptophane Cages with a C₁‑Symmetric Cyclotriveratrylene Unit

Two new hemicryptophanes combining a cyclotriveratrylene unit with either an aminotrisamide or a tris­(2-aminoethyl)­amine (tren) moiety have been synthesized. Although a conventional synthesis approach was used, the molecular cages obtained are devoid of the expected C₃ symmetry. NMR analyses and X-ray crystal structure determination showed that these hemicryptophanes exhibited C₁ symmetry due to the unusual arrangement of the substituents of the cyclotriveratrylene unit. This unprecedented arrangement is related to a change in the regioselectivity of the Friedel–Crafts reactions that led to the CTV cap. This constitutes an original approach to access enantiopure chiral molecular cages with low symmetry.