Studies On The Functionazliztion Of [60]Fullerene Using Pd(Ⅱ)-Catalyzed And HSVM Methods

Chemical modification is one of the most important research fields in the fullerene chemistry. Many functionalized fullerene derivatives have been synthesized hitherto, and have potential applications in materials, medical chemistry, and nanotechnolgy. Among these various functionalization methods, the functionalization of [60] fullerene using palladium-catalyzed and HSVM methods have attracted extensive attention in recent years. In this dissertation, we synthesized several new types of [60] fullerene derivatives through the two methods.1. The Pd-catalyzed heteroannulation of C6o with various N-benzyl sulfonamides via C-H bond activation affords C60-fused tetrahydroisoquinolines. In the presence of a Bronsted acid C60-fused tetrahydroisoquinolines are transformed to C60-fused indanes, of which the sulfonamide group can be removed or replaced with an aryl group.2. The Pd-catalyzed heteroannulation of C6o with N-(2-arylethyl)-sulfonamide derivatives via C-H bond activation afford scarce seven-membered-ring C60-fused tetrahydroazepines. In addition, the further transformtion and electrochemistry of the obtained C6o-fused tetrahydroazepines are investigated.3. The Pd-catalyzed reaction of C6o with various aryl iodides and N-methoxyl sulfonamides affords novel 1,4-adducts which bearing sulfonamide and aryl groups. The utility of the synthesized 1,4-adducts is further demonstrated.4. The Pd-catalyzed 1,4-addition of C60 with various aryl iodides and alcohols affords various 1,4-alkoxylated [60]fullerene derivatives. Compared with previous methods, this process is more concise and effective.5. The FeCl3-mediated solid-state reaction of C60 with N-benzhydryl sulfonamides afforded novel C60-fused indane derivatives in high regioselectivity under HSVM condition. In addition, the reaction mechanism and the electrochemistry of the obtained C60-fused indanes is investigated.