Palladium-catalyzed Oxalyl Amide Assisted Carbonheteroatom Bond Formation For Amine Derivatives

In recent years, transition-metal-catalyzed direct C–H functionalization reactions have become efficient approaches to construct the C-C and C-H bond. These development great enriched the protocols for syntheisis of complex structure of the drug and natural products. The directing strateg provide one of the most efficient approaches in realizing the high site selective C-H functionalization. Thus, it would be great important to develop a high activity, cheap, easily removable, transformable directing group. In this thesis, oxalyl amide directed palladium catalyzed high regioselective carbon-heteratiom bonds formation have been well developedThe main work of this paper includes the following four parts:The first part, a review for transition- metal-catalyzed C-H fluorination has been described.The second part, the progress of C-H silylation via transition-metal catalyst has been well reviewed.The third part, palladium-catalyzed selective ortho-C-H fluorination of oxalyl amide-protected benzylamines has been developed. The newly developed protocols are compatible of various functional groups, and the directing group was easily removed.The last part, palladium-catalyzed oxalyl amide directed silylation and germanylation of amine derivatives has been described. We report the first example of Pd(II)-catalyzed intermolecular silylation of C(sp~2)-H bonds in oxalyl amideprotected benzylamine and phenylethylamine to install an organosilicon moiety at the γ- and δ-positions. A broad range of functional groups were tolerated. Importantly, the γ-C(sp~3)-H silyation was also realized in moderate yield.Raw materials and products were identified by 1H-NMR, 13 C NMR and HRMS, and give a possible reaction mechanism.