Synthesis Of Fullerene-fused Carbocyclic Derivatives

Fullerene is the third allotrope of carbon discovered by mankind after graphite and diamond.Due to the unique structure and physical and chemical properties,fullerenes exhibit extensive application in light,electricity,magnetism and so on.As the vital research field of fullerene chemistry,functionalization plays an important role in regulating the physical and chemical properties of fullerenes,developing the new functional materials of fullerene derivatives,and promoting and expanding the application of fullerenes in different fields.Since the discovery of fullerene,its functionalization research has received extensive and continuous attention.And a series of fullerene derivatives were synthesized,including fullerene mono-addition derivatives,multi-addition derivatives,open-cage fullerenes,azafullerenes,and endohedral fullerenes and so on.Fullerene carbocyclic derivatives have shown a wide range of applications in the field of perovskite batteries and organic solar cells.In this dissertation,the main work focus on I₂ catalyzed the synthesis of[60]fullerene-fused 1,2-tetrahydrocarbazoles,Palladium-catalyzed the synthesis of novel fullerene-fused spirocyclic derivatives,and Palladium-catalyzed the synthesis of[60]fullerene-fused benzocarbazole derivatives.1.I₂ catalyzed the synthesis of[60]fullerene-fused 1,2-tetrahydrocarbazolesThe three-component carbocyclization reaction of[60]fullerene,ketone and indole catalyzed by iodine was reported,and a series of fullerene tetrahydrocarbazole compounds were efficiently constructed.The effects of various catalysts,substrate ratio and temperature on the reaction were discussed.Under the optimized reaction conditions,the substrate scope and the tolerance of functional groups were investigated.Various ketones,including cyclic or chain aliphatic ketones,and aromatic ketones,as well as various indoles,all successfully generate corresponding products in moderate to good yields under the current reaction conditions.Moreover,the methodology was also suitable for scale-up synthesis,proving the practicability of this method.Simultaneously,a series of control experiments were performed to make out the mechanism of the reaction.This transformation was the first case of metal-free catalyzed three-component annulation reaction of fullerenes.2.Palladium-catalyzed the synthesis of novel fullerene-fused spirocyclic derivativesA novel domino Heck/C-H functionalized strategy to construct fullerene spiro structure under transition metals catalysis was developed,which effectively delivered diversified novel[60]fullerene-fused spiro[4,5]/[5,5]derivatives.The effects of a series of palladium catalysts,ligands,bases and cosolvents on the reaction were screened.With optimized reaction conditions in hand,the substrate scope and the compatibility of functional groups were further examined.The results showed that o-iodophenol,o-iodoaniline,o-iodobenzylmalonate and 2-(2-iodophenyl)-indole alkylene derivatives can all undergo the tandem cyclization process by Heck/C-H reaction,providing a series of diversified nitrogen,oxygen and all-carbon[60]fullerene spiro[4,5]and[5,5]derivatives.Functional groups such as fluorine,chlorine,bromine,methoxy and esters are compatible,and the reaction showed a wide range of substrate scope and good functional groups tolerance.Moreover,the method was also suitable for the large-scale synthesis,providing an effective method for the synthesis of various fullerene spirocyclic derivatives.Based on the experimental results and literature research,a tentative mechanism for the reaction was illustrated.In addition,the electrochemical properties of fullerene-fused spirocyclic compounds was studied.The results showed that these fullerene spiro derivatives have good potential as electronically active materials to conduct related application research in the fields of OPV and PSC.3.Palladium-catalyzed the synthesis of[60]fullerene-fused benzocarbazole derivativesThe Palladium-catalyzed coupling carbocyclization reaction of 2-(2-iodophenyl)-1H-indoles and[60]fullerene was reported,providing a series of?-type expansion system rigid fullerene benzocarbazole derivatives.And the effects of different Palladium catalysts,ligands,bases and cosolvents on the reaction were screened.With optimized reaction conditions in hand,the substrate scope and the compatibility of functional groups were further evaluated.According to the experimental results and literature research,the possible reaction mechanism was proposed.