Study On C-H Amination Catalyzed By Transition Metals

Compounds containing C-N bonds are a class of molecules with important biological activities and are widely used in the biopharmaceutical industry.The economical,environmentally friendly,and simple construction method of C-N bond is the focus and hot spot in the development of organic synthesis.In the past,transition metal-catalyzed C-H bond activation amination has always been one of the important strategies for the construction of C-N bonds.At present,methods without transition metal involvement have also been reported.This paper is mainly divided into two parts.The first part briefly reviewed the research on the reaction of C-H bond activation and amination to build C-N bond,mainly including the following aspects:(1)Cu catalyzed the reaction of C-H bond activation to build C-N bond(2)Fe catalyzed C-H bond activation to build C-N bond Reaction(3)Pd-catalyzed C-H bond activation to build C-N bond reaction(4)Other metals catalyzed C-H bond activation to build C-N bond reaction(5)No transition metal catalyzed C-H bond activation to build C-N bond research.The second part is the experimental part,which mainly introduces my research work during the master’s period.3,4-Dihydroquinoxaline-2(1H)-one is a special nitrogen-heterocyclic skeleton,which has attracted widespread attention due to its remarkable biological activity.Among them,3-aminoquinoxaline-2(1H)-one is an important pharmacodynamic group,which has been widely used in clinical practice.Therefore,we studied the use of anhydrous copper acetate as a catalyst to catalyze 3,4-dihydroquinoxaline-2(1H)and primary and secondary aliphatic amines in air to achieve high-efficiency C(sp~3)-H aerobic amination of aromatic amines.The structured tandem reaction produces 3-aminoquinoxaline-2(1H)-one.The reaction substrate is well tolerated,and the quinoxaline aromatic ring containing electron-donating or electron-withdrawing groups can react well,and aliphatic amines can also react from cyclic derivatives to acyclic derivatives.In addition,the reaction is characterized by simple and mild reaction conditions,oxygen as the sole oxidant,and no external additives.