The Synthesis Of [60]fullerene Derivatives And Nitrogenous Heterocyclic Compounds

[60]Fullerenes are a class of electron-deficient cage molecules with sixty vertices and thirty-two faces,including twenty six-membered rings and twelve five-membered rings.They are used in physics,chemistry,biology,and materials.The special five-and six-membered ring alternately arranged structure makes fullerenes electron-deficient,and can undergo addition reactions with a variety of nucleophiles,to modify the surface of fullerenes.This has always been the research hotspots in the development of the history of fullerene The first part of this thesis studies the addition reaction of fullerenes with dicarbonyl compounds without transition metal catalysis.By changing the order of addition of iodine and fullerenes,a series of methylene groups can be synthesized efficiently and selectively.Method of bridging fullerenes and dihydrofuran cyclic fullerenes.In addition,tertiary enamide,as an emerging organic synthon,has been widely used in many nitrogen heterocyclic compounds.Compared with enamine,the nucleophilicity of tertiary enamide is reduced due to the presence of electron-deficient groups(acyl groups).However,the cross-conjugation system existing in the molecule can be adjusted by changing the substituents on the acyl group and the double bond,so that the lone pair of electrons on the nitrogen atom can be conjugated with the double bond,and the nucleophilicity of the double bond can be enhanced.The second part of this thesis is the study of the synthesis of azepine compounds based on the intramolecular nucleophilic reaction of tertiary enamides.Firstly,a tertiary enamide containing an aldehyde group in the molecule was designed and synthesized,and then a Konevenagel reaction with an active methylene compound was carried out to obtain a tertiary enamide containing a Michael acceptor in the molecule.Finally,an intramolecular Michael reaction occurred to efficiently prepare a series of Azepine compounds.The third part of this thesis is based on the nucleophilic tandem reaction within the tertiary enamide molecule to synthesize Erythrina alkaloid derivatives.Under the catalysis of Lewis acid and protic acid,the tertiary enamide containing electrophilic group and nucleophilic group in the molecule can synthesize the ring-closure product and its dehydration product with high efficiency and selectivity,respectively,constructing 6-6-5-6-6 Pentacyclic skeleton structure.This reaction is not only easy to operate,readily available raw materials,warm reaction conditions and high selectivity,but also provides a new method for synthesizing Erythrina alkaloids.