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

研究了Fulleroid/azafulleroid与反Bredt双键的亲电/酸性/亲核加成反应，以评价它们的区域选择性并发现新的反应。亲电性氧化剂mCPBA与富勒醇反应生成羟基酯产物，与C60氧化生成环氧化物。另一方面，氮杂氟内酯的氧化优先导致氮桥的氧化，然后氧化脱氨得到纯净的C60。氮杂芳烃的酸催化芳基化反应生成单芳化/五芳基化产物，这依赖于氮杂氟烷中抗Bredt烯胺部分的两亲碱性。此外，由于氮与镁的配位作用，格氏试剂与氮杂氟烷酮的亲核加成反应具有很高的区域选择性。

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.