Study On The Pd（OAc）₂Catalyzed Reactions Of[60]Fullerene

Fullerene chemistry has been intensively studied over the past30years. Among the various types of reactions for the functionalization of fullerene, transition metal salts promoted and catalyzed reactions have provided useful methods for the preparation of a wide range of functionalized fullerene derivatives. Although the reactions catalyzed by palladium have found widespread application in organic synthesis, there are only a few examples of them employed palladium complexes in fullerene chemistry. Reactions catalyzed by palladium continues to be a hot and fantastic arena in fullerene chemistry because of their high efficiency in constructing multiple new chemical bonds, thus leading to various complex structures in one step. This thesis mainly focuses on the Pd-catalyzed reactions of C6o with various organic compounds.In Chapter1, we simply reviews the recent development of transition metal salts promoted and catalyzed reactions of C6o and concluded the palladium catalyzed reaction of fullerene is the frontier of the functionalization chemistry of fullerene.In Chapter2, we assume the possibility of sulfonic acid group-directed C-H activation and try to utilize it for the functionalization of fullerene. The electron-deficient aryl ring of arylsulfonic acids is less prone to the C-H activation step compared to that of aryl carboxylic acids. We have addressed this challenge, and report the synthesis of sultones by Pd-catalyzed reaction of arylsulfonic acids with C60via unprecedented sulfonic acid groupdirected C-H bond activation.In Chapter3, we further expand the scope of this Pd-catalyzed sulfonic acid group-directed annulation reaction. We discover simple arenes can also be utilized to functionalize arylsulfonic acids and affords aromatic sultones under similar conditions. Our one-pot synthesis of aromatic sultones using very cheap and easily available starting materials afforded comparable or higher yields than the total yields from multi-step procedures, demonstrating the advantage of our protocol involving multiple C-H functionalizations.In Chapter4, we have attempted the Pd-catalyzed coupling reaction between C6o and thiophene derivatives. We achieve the Pd-catalyzed cross coupling and acetoxylation of C6o with thiophene, furan derivatives in the presence of AcOH. A series of heteroaryl and acetoxyl substituted1,2-C60compounds have been prepared and characterized. In addition, ferrocene can also undergo similar Pd-catalyzed oxidative coupling reaction with C60.Direct cross-coupling between these five membered aromatic heterocycles and C60have been realized for the first time.