Study On Group ? Transition Metal-Catalyzed C-H Activation Based On Oxadizole As Ditecting Group And Rhodium(?)-Catalyzed C-H Activation Polymerization Based On N-Nitroso As Ditecting Group

Group ? transition metal-catalyzed directed C-H activation,after years of development,has becong an efficient and flexible strategy of organic synthesis.In recent years,significant progress and extensive attention has been made in this field.This thesis mainly focuses on the reactions of new directing groups in Group ? transition metal-catalyzed C-H activation.The main contents include:The first chapter briefly reviews the related progress in Group ? transition metal-catalyzed directed C-H activation,mainly divides into two parts:Co(?)-catalyzed and Rh(?)-catalyzed.Each part includes reaction pattern and mechanism.The reaction pattern describes,still in C-H activation development,several nomal and some unusual reaction types.The reaction mechanism reviews the various of mechanism and examples.In the second chapter,we report a study of cobalt(?)-catalyzed internal oxidative annulations with alkyne via C-H activation based on oxadizole as directing group,and prepared a series of 1-amino isoquinolines.The catalytic reaction,which rarely uses opening/closing ring pattern,has significant advantages such as mild conditions,high efficiency,broad substrate scope and atom economy.According to the mechanism experiment including H/D exchange,D/H exchange,KIE,substrate competition and Co-complex experiments,a probable Co(?)catalytic cycle is proposed:Co(?)as the subject in catalytic cycle zatalyzes reaction based on oxadizole as directing group,then coupling with alkynes to give the products.And the cleavage of N-O bond engenders the Co(?),The third chapter,we report a study of rhodium(?)-catalyzed annulations with alkyne via alkenyl C-H activation based on oxadizole as directing group,and prepared a series of multisubstituted 2-acylamino and 2-amino pyridines.The catalytic reaction,which spreads to alkenyl C-H activation,has significant advantages such as high active and yield,wide substrate adaptability and good regioselectivity.According to the mechanism experiment including H/D exchange,D/H exchange,KIE,substrate competition,a probable Rh(?)catalytic cycle is proposed:Rh(?)as the subject in catalytic cycle zatalyzes reaction based on oxadizole as directing group,then coupling with alkynes to give the multisubstituted 2-acylamino,also we can get the 2-amino pyridines through change the solvent.The forth chapter,we report a study of rhodium(?)-catalyzed C-H activated polymeration based on N-nitroso as directing group,and prepared two polymers.Block copolymerization was carried out via two different monomers.The catalytic reactionhas significant advantages such as high active and yield.The optimized condition has been screened,and to give the good PDI.Subsequently,we have accomplished Block copolymerization for practical applicant.