Research On The Involvement Of Benzynes And Thiosulfonates In C-S Bond Construction Reaction

Organic sulfur compounds exist widely in the fields of pharmaceutical chemistry,biochemistry,organic synthesis and material science.In particular,sulfone compounds in organic sulfides and sulfilimines have good applications in drugs.Therefore,the construction of this kind of C-S bond in organic molecules is of great significance in pharmaceutical chemistry.As a highly active electrophilic reagent,benzyne is widely used in the construction of C-S bond.It is often intercalated with allyl sulfoxide,diaryl sulfoxide and sulfonyl fluoride to form C-S bond by one-pot reaction.This kind of reaction conditions are mild and easy to operate.This thesis mainly describes the participation of benzyne and thiosulfonate in the construction of C-S bond,which mainly includes the following two parts:The first part mainly introduces the synthesis of asymmetric aryl sulfone from benzyne and thiosulfonate without transition metal catalysis.The substrate universality of the reaction was studied by changing the substituents on the thiosulfonates and benzyne precursors,and 25 compounds were successfully constructed in medium to excellent yields.The reaction mechanism was studied by control experiment,isotope labeling experiment and gas chromatography-mass spectrometry（GC-MS）,and a possible reaction mechanism was proposed.In this experiment,the reaction was also studied on the gram scale,and the yield was 93%.In this experiment,a new method for rapid construction of C-S bond without transition metal participation and mild reaction conditions was developed.The second part introduces the study on the synthesis of N-sulfilimines by the three-component reaction of benzyne.A series of sulfilimines compounds were quickly constructed by the one-pot reaction of benzynes,thiosulfonates and sulfonamides.The reaction has good substrate universality.52 target compounds were synthesized with medium to good yields.The structures of all the products were confirmed by ¹H NMR,¹³C NMR and HRMS.The reaction can be enlarged on a gram scale and the yield is82%.This method provides a new way for efficient synthesis of N-sulfilimines under mild and non-transition metal catalysis conditions.