Study On Catalytic Oxidation Of C-H Bonds Induced By Triarylamine Radical Cation

This thesis mainly studies the aerobic oxidation reaction of glycine amide and glycine ester compounds, in the presence of catalytic cerium(IV) salt and triarylamine. In addition, we also studied the synthesis of a series of substituted quinoline derivatives via oxidative Povarov reaction of N-benzylanilines in the oxygen atmosphere under catalytic radical cations induced conditions. The details were listed below:(1) Catalytic Ce(IV) triggered sp3 C-H bond oxidation of glycine derivatives was achieved in the presence of catalytic tris(4-bromophenyl)amine, producing a series of quinolines, in which the generation of triarylamine radical cation is the key step to prompt the aerobic oxidation. Both intermolecular and intramolecular reactions occur smoothly, showing good generality towards the synthesis of functionalized quinoline derivatives.(2) Oxidative Povarov reaction of N-benzylanilines was realized under catalytic radical cation salt induced conditions. The mechanistic studies revealed that a radical intermediate was involved in this catalytic oxidation. This method provides a new way to synthesize 2,4-diarylquinoline derivatives.(3) A direct construction of pyrrolo[3,4-b]quinoline was achieved by catalytic radical cation salt inducing sp3 C-H bond oxidation.The polycycle product was formed via tandem CDC reaction, Friedel-Crafts reaction, and aminolysis.(4) The construction of important pharmaceutical skeleton-isatin was achieved through catalytic radical cation salt inducing Csp3-H functionalization of glycine amides and its derivatives.