Synthesis Of [60]Fullerene-fused Dihydropyrrole And Tetrahydrocarbazole Derivatives

Fullerene derivatives have shown a broad range of applications in materials science,electronic devices,and biomedicine.Therefore,functionalization of fullerenes has attracted significant attention,and numerous different classes of fullerene derivatives were prepared over the past three decades.The introduction of versatile functional groups and structural units on the fullerene core is useful for modifying its physicochemical properties,including its solubility,energy level and electron affinity,thereby providing important opportunities to exploit these different properties for expanding their applications in related fields.Therefore,the development of new and effective methods for continuously creating scarce and novel fullerene derivatives is of crucial importance.This paper aims at silver?I?-mediated the synthesis of [60]fullerene-fused dihydropyrrole derivatives and DDQ-mediated the synthesis of [60]fullerene-fused 1,2,3,4-Tetrahydrocarbazole derivatives.?1?Silver?I?-mediated the synthesis of [60]fullerene-fused dihydropyrrole derivativesWe have developed a silver?I?-mediated three-component annulation reaction of [60]fullerene,sulfonylhydrazones,and nitriles: leading to diverse disubstituted [60]fullerene-fused dihydropyrroles.We explored the influence of different reaction conditions through screening different silver salt and bases.Under the optimal conditions,we extend the series of sulfonylhydrazones and nitriles to investigate the influence of different substituent.At last,the reaction mechanism was studied.In the present study: a series of scarce and novel diverse disubstituted fullerene dihydropyrrole derivatives are first synthesized via a simple and efficient metal-based multicomponent reaction;the activation of the nitrile by Ag?I?is crucial for the success of this transformation,and is the first example of organic transformation involving silver-activated nitriles;the annulation reaction is flexible with regard to functional groups,and is also applicable to the synthesis of fullerene-based macromolecules.?2?DDQ-mediated the synthesis of [60]fullerene-fused 1,2,3,4-Tetrahydrocarbazole derivativesRecently we have developed a DDQ-mediated directly oxidative dehydrogenation reaction of indole derivatives and C₆₀ that leading to [60]fullerene-fused 1,2,3,4-Tetrahydrocarbazole derivatives.We explored the influence of different reaction conditions through screening different oxidant,solvent,cosolvent.Under the optimal conditions,we extend the series of indoles substrates to investigate the influence of different substituent.Finally,the reaction mechanism was studied.we herein present a direct metal-free oxidative dehydrogenative carboannulation reaction access to scarce C₆₀-fused tetrahydro-carbazole derivatives under simpler reaction conditions with a wide range of substrate scope and exceptional functional group compatibility.