Radical-Mediated Functionalization Of Unactivited Olefins,Conjugated Polyenes And [1.1.1] Propellane

Radical-mediated functionalization methodology provides an important way for the introduction of functional groups into organic molecules.This strategy affords handy means for the transformation of unsaturated bonds such as olefins and alkynes,as well as the construction or modification of drug and natural product molecules.The functionalization of organic molecules through the radical-mediated strategies has become a hot topic in organic chemistry recently.During the study of my Master degree,I mainly applied the free radical strategy into the heteroaryl silylation of unactivated olefins,the alkylation of conjugated polyenes,and the difunctionalization of[1.1.1]Propellane.The thesis contains four parts:The first part summarizes the recent advances of radical chemistry regarding the difunctionalization of unactivated olefins,the synthesis of substituted conjugated polyenes,and the functionalization of[1.1.1]Propellane.Besides,the basis and significance of my project will be introduced in this part.The second part introduces the heteroaryl silylation of unactivated olefins via radical-mediated distal heteroaryl migration strategy.The reaction possesses good substrate universality and functional group compatibility.The third part introduces radical-mediated Heck-type alkylation of conjugated polyenes.The reaction commences from polyenes in a mixed configuration which are easily prepared,and undergoes radical alkylation and oxidative deprotonation processes to obtain stereoconvergent multi-substituted polyenes.The reaction has mild reaction condition and good functional group tolerance.The fourth part introduces the radical-mediated difunctionalization of[1.1.1]Propellane.A series of disubstituted cyclo[1.1.1]pentane derivatives were synthesized by simultaneously introducing alkylheteroarylsulfone and bromine into the molecular framework.This reaction exhibits excellent atom economy.