The Direct Construction Of(fused)heterocyclic Structures Via The Functionalization Of Amines With Methyl Ketones Sp~3 C-H Bond

N-containing compounds are ubiquitous among biologically active molecules,natural products,and material sciences.The development of green,atom-economic,and sustainable methods to build N-containing compounds has always been a fascinating topic.The low cost and wide variety of commercially available anilines is highly attractive to be used as starting materials for the synthesis of N-containing compounds.Recent advances have focused on the C-H/N-H functionalization in anilines for the synthesis of N-containing compounds,especially through the direct functionalization of C-H/N-H in aniline with sp3 C-H.In this thesis,the diamination of methyl ketones and primary anilines were used as the research objects in I2-DMSO system.Aryl methyl ketones would be converted in situ to a-iodoacetophenone,phenylglyoxal.The active intermediates phenylglyoxal could be captured by aniline to different intermediates a,a-diaminoketone at different conditions.According this process,a novel and effective synthesis strategy was proposed to construct imidazoles and 1,2-fused oxidoles,and the reaction mechanism was also studied.The main contents of this thesis include the following three parts:In the first chapter,an overview of the progress of primary anilines in the synthesis of nitrogen-containing compounds in recent years was first summarized.According to research status and our previous work,we proposed our research topic.In the second chapter,the Radziszewski reaction is an important method for the synthesis of imidazole in industry.Although the reaction has a certain development in recent years,the substrate mostly concentrated in the carbonyl compounds and aldehydes.This article summarizes the recent reports on Radziszewski reaction.We developed the novel Radziszewski reaction by the[2 + 1 + 1 + 1]cyclization reaction of aryl methyl ketone,primary anilines and p-toluenesulfonyl methyl isocyanide(TosMIC).The preliminary experimental results show that the reaction proceeds in situ to form stable C-acylimine,which then reacts with the amine formed in situ from TosMIC to afford intermediate a,a-diaminoketone via an in situ cross-trapping process.Finally,intermediate a,a-diaminoketone was oxidized and participates in cyclocondensation with another phenylglyoxal in-situ to provide the desired product.It is the first example that methyl ketones served as the a-dicarbonyl compounds and aldehydes in Radziszewski-type reactions,which extends the application of the Radziszewski reaction.In the third chapter,an overview of the progress of the functionalization of C-H/N-H in primary anilines with C-H in the synthesis of N-containing compounds.Based on our interesting in the oxidative coupling reaction of aniline with acetophenone in I2-DMSO system,and combined with the current state under metal-free conditions(mainly concentrated in forming single C-C or C-N bond),we have proposed a domino bicyclization approach via multiple sequential C-H functionalization for the synthesis of 1,2-fused oxindoles from methyl ketones and primary anilines.Mechanistic studies revealed that the key step involved an oxidative cross-coupling between in situ-generated phenylglyoxal and a,a-diaminoketone.This new method allows for multiple C-C and C-N bonds from primary anilines and methyl ketones to N-containing compounds.