Catalytic C-H Amination And Decarboxylative Amination Reaction Using Azidoformates As Nitrogen Source

Nitrogen is an important element in pharmaceutical molecules,natural products and organic materials,thus the construction of nitrogen containing structure remains the cutting-edge in organic synthesis.The common method to build C-N bond is the coupling between electrophilic carbon source and nucleophilic nitrogen source.Organic azides is a unique kind of electrophilic animation reagent which enjoys advantages as easy preparation and high atom efficiency.This article focus on the amination reaction using organic azides as nitrogen source.The content of this article can be divided into two parts:1,visible-light induced intramolecular C-H amination reaction;2,Cu(OAc)2 and DMAPcatalyzed intermolecular decarboxylative amination via azide migration pathway.In the first part of this article,we choose substituted phenyl azidoformates as substrates,visible-light induced intramolecular amination reaction occurrs via energy transfer pathway.The reaction possesses such advantages as mild condition,excellent chemoselectivity and nitrogen exist as the only byproduct.We successfully synthesized a series of 2-benzoxazolinone derivatives which are regarded as an important organic motif.Besides,the selectivity of triplet state free nitrene is proved by molecule engineering for the first time.The chemoselectivity of the reaction is observed to be alkyl olefin aziridination>>electron deficient olefin aziridination?C(sp2)-H amination>>C(sp3)-H amination.The second part of this article reports the decarboxylative C-N coupling between organic carboxylic acid and azidoformates.A series of primary,secondary and tertiary alkyl carboxylic acid,alkenyl carboxylic acid and aryl carboxylic acid can couple with azidoformates with Cu(OAc)2 and DMAP as catalyst.This catalytic system is applied in the late stage functionalization of several complex drug molecules.The results reveal that this method is possessed of broad applicability,excellent functional group tolerance and high atom efficiency.We consider that this method may have great potential in pharmaceutical chemistry and new drug discovery.Besides,this is the first report of decarboxylative amination via azide migration pathway.