Transition Metal-catalyzed Directing Group Assisted C?N Bond Formation Of N-Aryl Amides

The N-aryl amide is of great importance as this structural motif widely used in numerous biomedical,industrial applications and functional materials.The synthesis of N-aryl amides has attracted much attention of chemists.With the rapid development of biomedicine and other fields,it is necessary to synthesize N-aryl amides by efficient and convenient methods.There are two parts in this thesis,the C-N bond of N-aryl amides is constructed with the transition metal copper and nickel are used as catalysts and the relatively inexpensive triphenylbismuth and phenylboronic acid are used as arylation reagents,by activating the N-H bond with the assistance of quinoline and pyridyl groups.1.The C-N bond formation reaction of N-（quinolin-8-yl）benzamide is achieved by using triphenylbismuth as the arylation reagent and quinoline as the directing group under copper catalysis.The reaction proceeded in the presence of Cu（OAc）₂（40 mol%）,NaHCO₃（2.0 eq）in 1,4-dioxane（2.0 mL）stirring under air at 100℃for 12 h.This method have the characteristics of simple conditions,high yield,good selectivity and strong compatibility of functional groups.It provides a new idea for the construction of C-N bond of N-aryl amides with directing group.2.The C-N bond formation reaction of N-phenylpicolinamide is achieved by using phenylboronic acid as the arylation reagent and pyridyl amide as the directing group under nickel catalysis.The reaction proceeded in the presence of NiBr₂（20 mol%）,MnO₂（1.0 eq）,Na₂CO₃（2.0 eq）in 1,4-dioxane（2.0 mL）stirring under air at 60℃for12 h.This method has a medium to high yield and a wide range of substrates scope under non-toxic and relatively inexpensive nickel,which provides another new method for the C-N bond formation of N-aryl amide by using pyridyl as the directing group.