Synthesis Of 1-Fulleropyrrolidines Via Iron-Catalyzed Reaction

The functionalization of fullerenes plays an important role in fullerene chemistry.Functionalization can introduce different functional groups on the carbon cage of fullerene,which is of great significance for solving and improving the solubility of fullerenes and preparing fullerene-based carbon materials with different functions.Therefore,the development of different chemical methods that can modify fullerenes to realize the synthesis of fullerene derivatives with diverse structures and functions is an important topic for fullerene chemistry and synthetic chemistry.In this dissertation,the iron-catalyzed redox-neutral reaction of C₆₀withγ,δ-unsaturated oxime esters has been developed to prepare 1-fullerene-fused pyrrolidine derivatives,in which the nitrogen atom linkes to the fullerene skeleton directly.The optimal reaction conditions were determined by screening different iron salts,reaction temperatures,co-solvents and the loading amount of catalyst.Based on the optimal conditions,we extended a series of unsaturated oxime ester derivatives with different substituents at different positions,discussed the effects of substrate electronic effect,steric hindrance on the reaction,and the reaction mechanism was also investigated through control experiments.At the same time,we have tested the electrochemical properties of some representative 1-fullerene-fused pyrrolidine derivatives.The results show that these compounds exhibit three reversible redox potentials and have similar LUMO energy levels to that of PCBM,indicating they can be used as acceptor materials in organic photovoltaic devices.In short,this redox-neutral reaction features with simple operation,environment friendly,broad substrate scope/high functional group compatibility as well as scale-up synthesis,and the obtained products can undergo further functionalization to prepare other types of fullerene derivatives.