| Both ketones and nitriles are important organic compounds,which are widely found in natural products,pharmaceuticals,materials and dyes.In addition,ketones and nitriels are also utilized as the fundamental raw materials in chemical industry because the carbonyl and cyano group can be readily transformed into many functional groups.The development of new reactions and methods for the synthesis of important functional molecules from readily available ketones and nitriles is an important research topic in organic synthesis.This thesis focuses on the ?-C-H bond functionalization of ketones or nitriles and their annulations,and the following results were achieved.Firstly,we have developed a new methodology for the synthesis carbamates via three components reaction of ketones,carbon dioxide and amines using nBu4 NI as catalyst and regarding TBHP as the oxidant.This was the first example of efficient constructing a diverse range of O-?-oxoalkyl carbamtes via ?-C-H bond functionalization strategy of ketones.Compared with previous methods,this methodology is atom-economical and environmentally friendly.Secondly,a base-promoted nucleophilic addition of arylacetonitriles with terminal alkynes for the synthesizing disubstituted acrylonitriles was discosed.The ?-C-H bond vinylation of cyano group of benzylic nitriles was achieved under mental-free conditions,providing a wide range of disubstituted acrylonitriles with exclusive region-and stero-selectivity,good functional group tolerance and wide substrates scope.Lastly,the copper-catalyzed [2+3] cyclization reaction of hydroxyl ketones with arylacetoniriles affording polysubstituted butenolides or oxazoles was also achieved.The reaction could be performed under very milder reaction condition with the formation of C-C,C-O and C-N bonds in one step.The method would find potential applications in organic synthesis since both butenolides and oxazoles widely exist in numerous natural products and pharmaceuticals. |
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