Radical Difunctionallization Of Olefins Via Remote Functional Group Migration And Amide-Mediated Functionalization Of Remote C(sp~3)-H Bonds

During the past years,radical-mediated remote functional group migration strategy has gained increasing attention.Many examples about radical-mediated distal functionalities 1,n-migration(n=4,5 or 6),have sprung up like mushrooms.The remote functional group migration strategy provides an efficient and convenient way to achieve difunctionalization of olefins and functionalization of remote inert carbon-hydrogen bonds.During the period of my Master,I mainly applied this strategy into the difunctionalization of unactivated olefins,thus respectively achieving the sulfonylheteroarylation and sulfony/trifluoromethyl alkynylation of olefins.In addition,regioselective C(sp3)-H bonds heteroarylation of amides proceeded readily via remote hydrogen-atom transfer(HAT)mediated by amidyl radical.The dissertation is divided into the three sections.The first part introduces sulfonylheteroarylation of unactivated olefins via radical-mediated distal heteroaryl migration to construct a set of distally difunctionalized aliphatic ketones.The transformation features good functional group tolerance,broad substrate scope and easy operation.The second part introduces sulfony/trifluoromethyl alkynylation of unactivated olefins via radical-mediated distal alkynyl migration to construct distally difunctionalized aliphatic ketones.The method features mild reaction conditions,broad substrate scope and good functional group tolerance.The last part introduces C(sp3)-H bonds functionalization of amides via remote hydrogen-atom transfer mediated by amidyl radical.The amidyl radical directly generated from N-H bonds of amide triggers 1,5-HAT process to form the alkyl radical,which then reacts with heteroarene to furnish the final product.The method features metal-free,broad substrate scope and good functional group tolerance.