A new approach towards the synthesis of the elusive heterofullerene C 58 N 2 is presented. The synthetic strategy is based on the intramolecular 1,3-dipolar cycloaddition of a spacerlinked azide to a monoazaheterofullerene (C 59 N) core. Since this cycloaddition can theoretically result in 16 different isomeric products, the design of the spacer moiety was based on extensive molecular modelling. Two fundamental synthetic routes towards suitably functionalized C 59 N derivatives were designed and carried out. Subsequent one-pot experiments, each making use of the same conditions as had previously