Study On Radical Trifluoromethylthiolation And Cascade Iodo-cyclization Reactions

In this thesis,iodine mediated tandem ring isomerization and trifluoromethylthiolation reactions have been researched,mainly including the following three chapters.Chapter one:In the first chapter,a literature review of the trifluoromethylthiolation reaction is carried out.According to the classification of trifluoromethylthio reagents,it is divided into free-radical,electrophilic and nucleophilic trifluoromethylthiolation reactions.Free radical reactions are mainly involving?SCF₃ reactions.At present,there are two main methods for generating?SCF₃:one is that AgSCF₃ produces?SCF₃ in a strong oxidant system;the other is that N-SCF₃ reagent produces?SCF₃ under visible light catalysis.The electrophilic reaction is the use of SCF₃⁺to achieve trifluoromethylation of olefins,alkynes,Grignard reagents,?-ketoesters,electron-rich aromatics,heterocyclic aromatics,boric acid,carboxylic acids and other substrates.SCF₃⁺is mainly produced by O-SCF₃or N-SCF₃ reagent in reaction.The nucleophilic reaction is to use SCF₃^-to undergo a nucleophilic reaction on the substrate.The SCF₃^-comes from a metal or non-metal salt which containing SCF₃^-in reaction.Chapter two:In the second chapter,it is reported that a free radicals trifluoromethylthiolation-tandem cyclization reaction which is initiated by the carbon-carbon triple bond in the substrate o-propargyl aryl azide?or o-alkynyl benzyl azide?in a strong oxidizer and AgSCF₃ system.The new strategy synthesizes a series of SCF₃ substituted quinoline and isoquinoline derivatived by simultaneously constructing C?sp²?-SCF₃ bond and C-N bond in one step reaction.Chapter three:In the third chapter,it is proposed that a tandem ring isomerization reaction of1-ene-6,11-diyne substrates promoted by iodine.Using the synthetic method,a series of iodine substituted tetrahydrobenzo[f]isoquinoline derivatives were prepared.In this reaction,a carbonyl group and two new cyclic skeletons were formed in one step and four new bonds were constructed.The reaction is easy to operate,a wide application of substrates and can be scaled up to gram-level reactions.In addition,the iodine substituted product obtained in this reaction can be further derivatized.