The Novel Approaches To Construct Phenol And Isoquinoline Derivative Via The Ortho-sclective C-H Functionalization Of Benzylamines

The C-H bond functionalization provides an environmentally friendly and highly atomic approach to the construction of various organic molecules.Phenol derivatives are common and important component in many drugs,agricultural chemicals and polymers.They are also very important intermediates in organic synthesis.On the other hand,isoquinoline as an important skeleton is widely present in biologically active natural products,organic materials,drugs,and some important ligands,shows unique activities and functions.However,traditional methods for synthesizing these compounds are complicated and difficult,so it is of great significance to develop efficient and direct strategies.This paper mainly explored palladium(?)catalyzed ortho C-H bond functionalization of benzylamines,and provided a new simple and direct method for the synthesis of phenol and isoquinoline compounds.The main contents are as follows:In the first part,a series of reactions of transition-metal catalyzed C-H hydroxylation to construct phenol derivatives in recent years have been discussed.The research progress of various nitrogen-containing compounds and alkynes to construct isoquinoline skeleton have been introduced briefly.In addition,the reactions using vinyl acetate as a key substrate to construct heterocyclic compounds were also summarized.Finally,the research objective and direction of this paper were described.In the second part,a Pd-catalyzed,ortho-selective C-H hydroxylation of benzylamine assisted by Cbz-amide to synthesize phenol derivatives conveniently and efficiently has been developed.The bioactive heterocycles such as oxazine,2-arylquinazolinone and oxazoline were synthesized in an economical and fast way,which proved the application value of this strategy.In the third part,a Pd(OAc)2 catalyzed,ortho C-H allylation/oxidative cyclization reaction of oxalyl amide-protected benzylamine was developed.An efficient one-pot two-step method was developed to realize the direct construction of isoquinoline derivatives,which provided a concise and efficient new method for the construction of isoquinoline compounds...