Palladium- And Copper-Catalyzed Heteroannulation Of [60]Fullerene With Oximes

Since the gram-scale preparation of[60]fullerene was realized in 1990,the surface modification of[60]fullerene has attracted the attention of many scientists from all over the world.Various new types of fullerene derivatives have synthesized.Over the past decades,a lot of fullerene derivatives have been widely used in medicinal chemistry,photoelectronic materials and many other fields.Therefore,it is particularly important to synthesize new fullerene derivatives by different approaches.At present,the methods commonly used for the surface modification of fullerenes include nucleophilic reactions,cycloaddition reactions,radical reaction and so on.Transition metal salts such as manganese,copper,iron,silver,and palladium salts catalyzed or promoted reactions have recently been used in fullerene chemistry by taking advantages of high yield,good selectivity and mild conditionsfor the fullerene surface modification.Owing to the unique structure of-N-OH of the oxime compounds,the palladium-catalyzed CH activation and the copper-catalyzed radical reaction can be achieved,and the results of the two types of reactions are completely different.In this thesis,the palladium-and copper-catalyzed reactions of[60]fullerene with oximes have been investigated.The main work of this thesis includes the following two aspects:1.A palladium-catalyzed oxime-directed C-H activation reaction has been utilized to synthesize a seven-membered cyclic[60]fullerene-fused dihydrobenzooxazepines derivatives;then the formed seven-membered cyclic products can be further transformed into 1,2,3,4-and 1,2,3,16-adducts of[60]fullerene by electrochemical functionalization.2.A copper-catalyzed reaction of[60]fullerene with N-hydroxybenzimidyl cyanide has been explored,generating unexpectedly[60]fullerene-fused oxazoline derivatives.