A covalent organic cage compound acting as a supramolecular shadow mask for the regioselective functionalization of C.

A trigonal-bipyramidal covalent organic cage compound serves as an efficient host to form stable 1 : 1-complexes with C and C. Fullerene encapsulation has been comprehensively studied by NMR and UV/Vis spectroscopy, mass spectrometry as well as single-crystal X-ray diffraction. Exohedral functionalization of encapsulated C threefold Prato reaction revealed high selectivity for the symmetry-matched all--3 addition pattern.