Study On Radical Cascade Reactions Involving Alkenes And Alkyl Halides/Cycloketone Oxime Ethers

In this paper,the radical addition reactions of difluoroalkyl reagents,halogenated sugars and cycloketoxime esters with unsaturated double bonds were studied,including the following five chapters:Chapter IThis chapter is divided into two sections to introduce the progress of radical tandem reactions between difluoroalkyl reagents and unsaturated double bonds;The latest progress in the construction of C-glycosidic bonds through the free radical pathway using bromosugars in recent years;Research progress of carbon-carbon bond recombination strategy based on imino radical ring opening.Section one The unique fluorine effect of fluorine atom received extensive attention,which can effectively improve the physiological,chemical and physical properties of organic compounds.Especially the difluoromethylene,due to its special metabolic stability,the related research has developed rapidly in recent years.In this section,we using XCF₂CO₂Et as the source of difluoromethylene to summarize the recent studies on the series reaction of XCF₂CO₂Et with olefins.Section two As one of the three major components of the basic unit cell of life,carbohydrate compounds are an indispensable part of organism.In particular,C-glycoside derivatives are widely existed in drug molecules and natural products.Therefore,the modification of the C-glycoside backbone is of far-reaching significance.In this section,we will briefly summarize the recent progress in the construction of C-glycoside skeleton by different catalytic systems based on bromosugar radical pathways.Section three Cyanoalkyl skeletons are widely existed in biologically active molecules,such as drug molecules and natural products.Therefore,the efficient method for introduction of cyanoalkyl groups into compound molecules is of great significance in synthetic chemistry.In this chapter,the research progress of cyanoalkyl radical involved in free radical Heck,cyclization,bifunctionalization and heteroatomization to construct cyanoalkyl compound skeleton in recent years is briefly introduced.Chapter?In this chapter,a novel non-metallic catalytic system was developed to realize the difluoroalkyl radical cyclization of 1,6-enynes.In this reaction,two differently substituted difluoroalkyl cyclization products were synthesized by selectively using inorganic bases and organic bases.There is no need to add transition metal reagents in the system,which meets the development requirements of green sustainable chemistry.Chapter?In this chapter,the author continues the new method developed in Chapter 2.A series of CF₂/CF₃-substituted linear alkyne ketone derivatives were synthesized without metal by the migration of 1,2-alkyne group under mild reaction conditions.Chapter?In this chapter,the author describes a new type of visible light-induced palladium-catalyzed free radical Heck reaction of bromosugars with the participation of aryl olefins.The reaction has high regioselectivity and stereoselectivity,and can be used to prepare various substituted C-vinyl glycosides.Compared with previous strategies,this reaction has the advantages of simple raw materials and short reaction steps.This strategy has potential application value in the modification of drug molecules and natural products.Chapter?This chapter reports the synthesis of cyanoalkylsulfonyl indole and cyanoalkylamide by copper-catalyzed cyclic ketoxime ester radical ring-opening-cross-coupling and aryl migration strategy with the participation of activated olefin.By skillfully designing the substrate,the leaving group in the substrate is used as the reactant to realize the efficient utilization of atoms.