Study On The Tandem Cyclization Reaction Of Unactivated Olefins And Polychloromethyl Radicals(or Silicon Radicals)

This paper mainly describes a series of cascade cyclization reactions of polychloromethyl radicals(or silicon radicals)discovered by our group,which selectively produce various derivatives,such as polychlorinated isoquinolones,polychlorinated dihydroisoquinolones,polychlorinated dihydroquinolones,difunctional products,and silylated dihydroisoquinolones.The paper consists of the following four parts:The first chapter summarizes the research background of polychlorinated compounds and organosilicon compounds.In recent years,researchers at home and abroad have made a lot of studies and made great progress on polychlorinated compounds and organosilicon compounds.Our group summarizes the literature precedent study and develops new methods based on our previous radical work.In chapter two,the synthesis of polychlorinated isoquinolones and dihydroisoquinolones are described.Isoquinolones and dihydroisoquinolones are common N-heterocyclic compounds,which have good biological properties.Our group found that the reaction of unsaturated benzoamides and chloroform(CHCl₃)can produce polychlorinated isoquinolones;the reaction of unsaturated benzoamides with dichloromethane(CH₂Cl₂)can prepare polychlorinated dihydroisoquinolones.Our group optimized the reaction conditions,investigated the substrate tolerance,and obtained a series of target products.Finally,through varying polychloromethanes,both isoquinolinones,and dihydroisoquinolinones could be gained selectively under typical conditions.In chapter three,we describe the preparation of polychlorinated dihydroquinolones and the study of kharasch reactions.The polychloromethylated dihydroquinolones can be obtained by using N-aryl-3-buteneamide and chloroform(CHCl₃)as the substrate.The free radical kharasch addition reaction can be carried out between N-aryl-3-buteneamide and carbon tetrachloride(CCl₄).Our group studied a series of conditions optimization to get the best conditions,and also investigated the substrate scope to obtain various desired products.In chapter four,the preparation of silylated dihydroisoquinolones is introduced.Organosilicon compounds are widely used in organic chemistry,chemical engineering,biology,and pharmacy due to their unique physical and chemical properties.Gaven the importance of organosilicon compounds and dihydroisoquinolones and the superiority of free radical strategy,we developed a free radical strategy.A series of silylated dihydroisoquinolones were synthesized by the free radical reaction of silanes with unsaturated amides as the substrate.