Palladium-catalyzed Inert C-H Bond Arylation Of Aldehydes And Ketones

The C-H activation reaction is an important part of organic chemistry and was once called the "Holy Grail" in organic chemistry.Later,chemists achieved the activation of the C-H bond by participating in the transition metal catalysis.With the continuous development of the directing group,chemists have realized the transition metal-catalyzed C-H bond activation reaction through the transient directing group.However,the universality and practicability of the reported guiding base still have certain limitations.Therefore,continuous design and search for a class of transient directing groups with high universality is of great significance for the C-H activation reaction.This paper consists of the following four parts:The first chapter mainly reviews the research progress of catalytically inert C-H bonds based on guided metal in recent years.The design and utilization of activated metal catalytically inert C-H bond directing groups are highlighted.It is expected that some strategies and experience will be obtained to provide guidance for the synthesis of aldehydes and ketones.The second chapter mainly introduces the development of a method for the activation of Pd-catalyzed aliphatic C(sp3)-H bond catalyzed by amino amide as a transient directing group.A new class of aminoamide-based transient directing groups was designed and synthesized,and its activation of inert C(sp3)-H bond was systematically studied.The experimental results show that the reaction has good functional group compatibility,substrate universality and regioselectivity.The yield of?-C(sp3)-H bond arylation product of aliphatic aldehyde is up to 82%,and gives high diastereoselectivity(dr>20:1);The yields of ?-C(sp3)-H bond arylation product of the aliphatic ketone was also up to 82%.The mechanism of C-H bond activation of this reaction was speculated by previous experimental studies and literature reports.The third chapter is the experimental part,which introduces some conventional experimental operations and experimental instruments,as well as the synthesis methods of catalysts and aliphatic aldehydes and ketones arylation products.Finally,the synthesized catalysts,aliphatic aldehydes and ketones arylation products were structurally characterized.