DDQ-mediated Functionalization Of Substituted Aniline

Carbon-carbon and carbon-hetero bond formation reactions are very important reactions in organic synthesis.As an important part of organic synthesis,chemists have been seeking efficient and economical methods for the construction of carbon-carbon and carbon-hetero bonds.At present,the activation of carbon-hydrogen bonds has attracted widespread attention.The selective activation of carbon-hydrogen bonds is an important issue in organic chemistry.The research and application of chemical reaction selectivity have made great progress,but there are still many defects and problems,such as using metal or excessive catalyst,the more demanding reaction conditions,which make us seek a greener method.In this dissertation,the activation of carbon-hydrogen bonds at different positions of alkyl-substituted anilines is reviewed.By summarizing the laws,a rational and selective synthetic route was designed.The functionalization of N,N-disubstituted aniline was achieved by DDQ oxidation induction.Thesis research mainly obtained the following results:1.We developed a transition-free metal-mediated oxidation induction strategies for efficient and selective C-H bond functionalization of N,N-dimethylaniline derivatives.First,using the methyl group of N-methylaniline as a carbonyl source,formylated C-H bond activation is achieved at the para position of N,N-dimethylaniline.In addition,based on an understanding of this mechanism,this method is also used to construct C3-formylation of indole with 4-methoxy-N,N-dimethylaniline as a carbonyl group.2.Using inexpensive and easily available saccharine as a nitrogen-containing nucleophile,the formation of sp~3 C-N bond was achieved under the oxidative induction of DDQ.And in the presence of TBN,a catalytic amount of DDQ catalytic cycle is achieved.This method not only realizes the rapid and efficient synthesis of carbon-nitrogen bonds,but also achieves the gram-grade synthesis standard.