C-C And C-N Bond Construction Reactions Of Naphthols And Indoles With Aryl Triazenes

The aryltriazene is often used as a synthetic intermediate in organic synthesis because it has multiple active sites.It is also widely used as a substitute for arylazo reagents and arylation agents.Due to its unique structure,aryltriazene is often used as a substitute for aryl diazonium salts to react with other reagents to construct new C-C bonds or C-N bonds.In the previous work,the same stable synthon was rarely used in the method of constructing C-C bond or C-N bond to realize the construction of these two bonds at the same time.Aryltriazene optimizes the instability of aryl diazonium salts due to its unique structural properties of the triazene compound.In this paper,aryltriazene was used as an electrophile to realize the azotization of naphthol nucleophile,the C2 arylation and C3 azotization reactions of indoles nucleophiles were also achieved.The first part:the aryltriazene is used as the aryl source and the azo source to classify its reaction.The reaction of aryltriazene as an aryl source and azo source is summarized.The second part:naphthol and aryltriazene as the reaction substrate,HPF₆ as the promoter,trifluoroethanol as the reaction solvent,the reaction is carried out at room temperature to give the azo nitride product of naphthol in a yield of up to 99%.The practicability of the reaction was further confirmed by post-sulfonamide drug modification and dual diazenylation of 5-amino-1-naphthol.In the third part:an efficient and regio-divergent method for both C2 arylation and C3 diazenylation of C2,C3-unsubstituted indoles with arytriazenes has been developed.The reaction was carried out with HPF₆ as the promoter at room temperature under open-flask and mild conditions.C2 arylation was successfully achieved in the presence of Pd?OAc?₂ catalyst and DMF solvent under mild conditions.Meanwhile,3-arylazoindoles was obtained with TFE as solvent under metal-free and mild conditions.Notably,the practicability of the protocol was further demonstrated via gram-scale operations and late-stage modification.In summary,in this thesis,aryltriazene was used as a diverse synthon to realize the diazenylation reaction of naphthol.Moreover,both C2 arylation and C3diazenylation of indoles with arytriazenes were successfully tuned with promoter,solvent and catalyst.A simple method is provided for the synthesis of such compounds.