Study On The Coupling Reaction Of Metal-Catalyzed Amide Derivatives With Thioethers

Amide derivatives have a wide range of applications in industry and medicine,and their new transformations are important in both practival and theoretical aspects.In this thesis,the coupling reactions of N-acyloxy substituted amide derivatives with phenyl allyl sulfide de-rivatives under different metal catalysts were studied.The main work includes the following two aspects:?1?Study on iron-catalyzed coupling reactions between N-acyloxy substituted amide derivatives and thioethers.Under the assistance of FeCl₂,the amide precursors could be transformed into metal-nitrene intermediate,which reacted with phenylallyl sulfides to form a series of amide derivatives containing N-arylthio group and N-allyl group.The advantages of the reaction include cheap and easily available catalyst,no external ligands and additives under mild conditions at room temperature;however,the reaction still has shortcomings,such as relative narrow substrate scope,using of unhydrous solvent,nitrogen protection,and a large amount of catalyst loading.?2?Study the ruthenium catalyzed coupling reactions between N-acyloxy substituted amide derivatives and thioethers.When using RuCl₂?PPh₃?₃ as the catalyst,AgOAc as the additive,and benzohydroxamic acid as the ligand,the coupling reaction is quite effective and to be completed in 10 min at room temperature.It was proved that benzohydroxamic acid played a crucial role in the reaction,and the structures for the by-products were characterized by NMR and GC-MS,which provided a basis for mechanism discussion.The method is a further improvement of the iron-catalyzed reaction,which greatly advances the reaction efficiency and the substrate scope.