One-Pot 1,4-Difunctionalization of C60 with H-Phosphonates and Nucleophiles via Anion/Radical Cascade.

An unsymmetrical 1,4-difunctionalization of C60 using H-phosphonates and nucleophiles─which involves a one-pot stepwise process of nucleophilic addition, protonation, and oxidative coupling─has been developed for the synthesis of a wide range of 1,4-(phosphonyl)(organo)[60]fullerenes. Furthermore, a cascade pathway involving fullerene anions and fullerene radicals leading to 1,4-diorgano-[60]fullerenes has been revealed by the capture of the phosphonate-substituted fullerene radical by BHT.