Difunctionalization Of Unactivated Olefins And Alkynes Activation Of C(sp~3)-H Bonds T Through Radical-Mediatted Distal Functional Group Distal Migration

The strategy of radical-mediated distal functional group migration provides an effective way to introduce functional groups in organic molecules.Due to the wide applicability and high atom economy,this strategy has attracted much attention from synthetic chemists.During the study of my Master degree,I mainly applied this method into the difunctionalization of unactivated olefin and the regioselective activation of C(sp3)-H bonds,thus respectively achieving not only the azidoheteroarylation and monofluoroalkyl alkynylation of olefins,but the cyanation of C(sp3)-H bonds.The dissertation is divided into the four sections.The first part summarizes functionalization of olefins and C-H bond based on radical-mediated distal migration.In addition,the basis and significance of my project is introduced in this part.The second part introduces azidoheteroarylation of unactivated olefins by the strategy of radical-mediated distal heteroaryl migration to construct distally difunctionalized aliphatic ketone compounds.The reaction exhibits wide application range and good functional group tolerance.The third part introduces difunctionalization of both activated and unactived olefins via docking-migration tactic.Monofluoroalkyl alkynylation of olefins can be obtained by well-designed dual-function reagents.The last part introduces activation of inert C-H bond via cyano migration.The alkoxy radical directly generated from tertiary alcohol triggers the successive 1,5-HAT and cyano migration.The mild reaction exhibits broad substrate scope and specific regioselectivity.