Sequential Tether‐Directed Synthesis of New [3 : 2 : 1] Hexakis‐Adducts of C(60) with a Mixed Octahedral Addition Pattern

A new concept for the regioselective synthesis of [3 : 2 : 1] hexakis‐adducts of fullerene C(60) was developed. Based on sequential tether‐directed remote functionalizations, chiral [3 : 2] pentakis‐adducts with an incomplete octahedral addition pattern were synthesized via stepwise cyclopropanation of C(60) with suitable macrocyclic tri‐ and bifunctional cyclomalonate tethers. The four resulting stereoisomers were isolated using chiral HPLC. The corresponding pairs of enantiomers show mirror image behavior in their CD‐spectra. The pentakis‐adducts served as suitable building blocks for the spatially controlled synthesis of mixed hexakis‐adducts. Implementation of functional group‐bearing monomalonates afforded octahedral [3 : 2 : 1] hexakis‐adducts suitable for the construction of larger molecular and supramolecular fullerene architectures in excellent yield.