Study On Copper Catalyzed / Promoted Difunctionalizations Of Alkenes

The direct difunctionalization of alkenes—means the incorporation of two functional groups onto a carbon–carbon double bond,which has always been the research hotspot in organic synthesis owing to its simple,efficient and extensive applications in organic synthesis.After years of efforts by chemists,at present,various strategies such as epoxidation,dioxidation,aminoxidation,and diamination have been developed through this strategy.In this paper,mechanistically,we divide it into two types-transition-metal-catalyzed nucleophilic difunctionalization and radical difunctionalization,and made a summary report separately.At the same time,the oxysulfonylation,oxysulfenylation,and diamidation of unactivated alkenes developed by our group were also described in detail.This thesis is composed of four chapters: In chapterⅠ,we divided two parts,which are(1)The development of transition metal catalyzed difunctionalization of alkenes were reviewed,focusing sharply on difuncionalization of alkenes catalyzed by palladium and copper;(2)The research progress of radical difunctionalization of alkenes were summarized in detail,mainly introducing the intermolecular and intramolecular radical difunctionalization of alkenes.In chapter Ⅱ,an efficient copper-catalyzed oxysulfenylation of alkenoic acids with benzenethiols via radical pathway was developed.The transformation can be carried out under air,and we use the oxygen in the air as a mild oxidant.We synthesized a range of sulfenylated lactones,through radical addition and intramolecular nucleophilic addition.This reaction further enriches the example of the construction of C-S bonds through the reaction of sulfur radicals with alkenes substrates under the catalysis of transition metals.In chapter Ⅲ,we have developed an efficient and practical copper-mediated oxysulfonylation reaction of alkenyl oximes with sodium benzenesulfinates for the synthesis of sulfonylated isoxazolines.we confirmed that the reaction not only may be a radical addition process,but also an electrophilic addition process,by adding radical scavenger(TEMPO and 1,1-Diphenylethylene).This reaction proceeds readily at room temperature.Meanwhile,this novel transformation used easily available and stable sodium benzenesulfinates as ideal sulfone reagents.In chapter Ⅳ,we have developed a copper-catalyzed intra-/intermolecular alkene diamination reaction between β,γ-unsaturated hydrazones and simple amines.This transformation offers a common and efficient method to access a variety of nitrogen-containing pyrazolines,which are valuable building blocks in organic synthesis and medicine.This reaction is easy to be conducted under mild conditions,without additional oxidant.