| In 2014,Our research group reported the synthesis of 3-diazoindolin-2-imimes and used them for the study of the chemistry of a-amidino rhodium carbene.Thus,a series of rhodium catalyzed reactions had been carried out and a number of indole-containing compounds were synthesized.In this thesis,we developed two types of reactions based on 3-diazoindolin-2-imines.The first reaction is the acid catalyzed reaction between 3-diazoindolin-2-imines and electron-rich arenes.The other reaction is the Rh2(HFB)4 catalyzed reaction between 3-diazoindolin-2-imines and allyl alcohol.1.A concise and practical approach to 3-aryl-2-aminoindoles from 3-diazoindolin-2-imines and electron-rich aromatic compounds in the presence of trifluoromethanesulfonic acid was developed.In this reaction,the protonation of 3-diazoindolin-2-imine results in the formation of a diazonium salt.Then denitrogenation occurs to provide a cation intermediate.Finally,the Friedel-Craft arylation between the cation intermediate and electron-rich arenes happens and affords the products.Compared with the published methods for the synthesis of 3-aryl-2-aminoindoles,this protocol is metal-free and the reaction conditions are much milder.Moreover,the reaction tolerated a broad range of electron-rich arenes,including thiophenes,pyrroles,indoles,substituted benzenes,and naphthalenes.2.A new method for the preparation of hemicyanine dyes was developed,which was offered by the reaction between 3-diazoindolin-2-imines and allyl alcohol catalyzed by Rh2(HFB)4.In the presence of a rhodium(II)catalyst,the 3-diazoindolin-2-imine is converted into ?-amidino rhodium carbene.Then,a O-H insertion occurs and offers an intermediate,which undergoes an intramolecular rearrangement to offer the final product.In recent years,hemicyanine dyes palyed an important role in nucleic acid,proteins,cell detection and immune analysis.The thesis offers a one-step method for the preparation of hemicyanine dyes,and it could be useful in the future research. |
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