Copper-catalyzed Synthesis Of Fulleropyrrolidines And 1-fulleropyrrolines

The unique electronic and optical properties of fullerenes make them find a broad range of applications encompassing nanoscience,electronic devices,supramolecular assembly,biomedicine and more.To enable the effective application of these properties,chemical functionalization of fullerenes is necessary.On the one hand,it can effectively improve physical properties and chemical properties,such as solubility and electronic affinity by introducingdifferent organic functional units.On the other hand,it provides a multitude of opportunities to create novel fullerene-based functional materials for expand the range of potential applications by the exploration and development of new reactions of fullerenes.Therefore,functionalization of fullerenes represents an important and challenge subject in fullerene chemistry.This dissertation aims at the new recation of copper salt-catalyzed by C₆₀ and ?-N,O and S-substituted oxime acetates derivatives forthe synthesis of [60]fullerene-fused unsymmetrical fulleropyrrolidines and [60]fullerene-fused diverse disubstituted 1-fulleropyrrolines.?1?CuI-catalyzed the synthesis of [60]fullerene-fused unsymmetrical fulleropyrrolidinesWe have developed a new reaction of CuI-catalyzed internal-oxidant N-heteroannulation reaction of [60]fullerene with ?-N-substituted oxime acetates derivativesfor the synthesis[60]fullerene-fused unsymmetrical fulleropyrrolidines.Firstly,readily available and inexpensive Cu I to be the best catalystthrough widely screening different ferric salts andcopper salts.Secondly,the infiuence of different temperature and cosolvent were investigated.With the optimal system in hand,we next examined the substrate scope of this annulation reaction.A broad range of ?-N-substituted oxime acetates derivatives with different substituents at different position was employed.The effects of steric hindrance and electron effect on the reaction were investigated,and the possible reaction mechanism was proposed by the control experiment.?2?CuS-catalyzed the synthesis of [60]fullerene-fused monosubstitued and diverse disubstituted 1-fulleropyrrolinesWe have developed a new reaction of CuS-catalyzed internal-oxidant N-heteroannulation reaction of [60]fullerene with ?-O,S-substituted oxime acetate derivatives for the synthes of [60]fullerene-fused monosubstitued and diverse disubstitued 1-fulleropyrrolines.Firstly,the optimal system was decided through widely screening different copper salt,cosolvent,temperature and time.To evaluate the generality of this catalytic system,we subsequently employed a series of ?-O,S-substituted oxime acetate derivatives with different organic functional units.Finally,the reaction mechanism was discussed by a series of control experiments and the theoretical calculation.