Study On The Preparation Of Novel C₆₀ Derivatives Catalyzed By Transition Metal Palladium/Copper

Because of its unique geometrical shape and chemical properties,the chemical derivatization of fullerene is an important frontier of active research.In the past thirty years,fullerene chemistry has been widely investigated and developed.Chemical modification of fullerene can not only maintain the unique characteristics of pristine fullerene,but also can tune its solubility,energy level,molecular interactions,and surface energy.These merits endow functional fullerenes to be application in medicine,photovoltaic de vices,biomaterials and so on.And transition metal salts catalyzed（mediated）reaction with fullerene could enrich and expand the derivatization of fullerenes by provided a lot of powerful methods and measures.Although the strategies have a wide range of applications in organic synthesis,only relatively few examples are used in fullerene chemistry.Copper and palladium salts as catalysts with characteristics of high efficiencies to achieve a multi-step C-H bond activation,which can be constructed conveniently for the formation of C-C,C-N,C-O bonds.Based on the above factors,this paper aimed at establishing methodologies about the reaction of fullerene with organic groups catalyzed（mediated）through copper or palladium salts to synthetize novel fullerene derivatives.The main work includes the following two aspects:In the first part,we have designed the possibility of using dimethylanilines as substrates to react with C₆₀ through copper salt-mediated sp3 C-H bond activation.A cross-dehydrogenative coupling（CDC）process under CuCl₂-mediated N,N-dimethylanilines with [60]fullerene to achieve a series of novel [60]fullerene-fused tetrahydroquinolines through sp2-sp3 C-H bond activation.And the electrical properties of these derivatives have been expl ored.In the second part,we have designed the possibility of using aryl formyls as directing group to achieve sp2 C-H bond activation with C₆₀ via Pd-salts catalyzed.In this system,Cu（OAc）₂ and Ag₂ O have been selected respectively as oxidant under Pd（OAc）₂ catalyst into the [60]fullerene reaction,which we have introduced the aryl β-diketones and isobutylbenzophenones as substracts.Under this process,we have synthesized varieties of new C₆₀-tetrahydrofurans as well as rare monohydroxylated fullerenols.And the electrical properties of C₆₀-tetrahydrofurans have been studied.