Exploration for Regioselective fullerene derivatives via of synthetic intermediates fulleroid/azafulleroid having high reactive anti-Bredt double bonds

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Electrophilic/acidic/nucleophilic additions to fulleroid/azafulleroid with anti-Bredt double bonds were investigated to evaluate their regioselectivity and discover novel reactions. Electrophilic oxidant mCPBA reacted with fulleroid to give hydroxyester products while oxidation with C60 gave epoxides. On the other hand, the oxidation with azafulleroid preferentially lead to the oxidation of nitrogen bridge, followed by oxidative deamination to give pristine C60. Acid catalytic arylation of azafulleroids lead to monoarylated/pentakisarylated products, depended on the ambident basicity of anti-Bredt enamine moiety of azafulleroids. Moreover, nucleophilic addition of Grignard reagents with azafulleroid gave highly regioselective adduct due to the nitrogen coordination with the magnesium.