Alkenylation Of Remote C(sp~3)-H Bonds And Oximino-Alkylation Of Olefins Through Radical-Mediated Migration Reaction

Aliphatic C(sp3)-H bonds are the fundamental structural units of organic molecules,and the direct functionalization of aliphatic C(sp3)-H has extraordinary significance in modifying and synthesizing complex organic blocks.However,the bond dissociation energy(BDE)of the C(sp3)-H bond is about 100 kcal/mol,which makes it challenging to transform this bond directly.In recent years,chemists have realized the regioselective activation of the C(sp3)-H bonds via transition-metal catalysis and radical-mediated hydrogen-atom transfer(HAT)progress.In organic chemistry,the alkylation of olefins can build C-C bonds effectively.The study of new alkylation strategies has always attracted the attention of chemists.During the research of my Master degree,I mainly focused on alkenylation of C(sp3)-H Bonds and olefinic alkylation via radical-mediated functional group migration,which develops an efficient and novel methodology for the synthesis and conversion of substituted alkenes.The dissertation is divided into the four sections.The first part summarizes research background about alkenylation of C(sp3)-H bonds and olefinic alkylation involving transition-metal and radical mediated,from which the basis and significance of my project derives.The second part introduces that radical mediates alkenylation of remote C(sp3)-H.Alkenyl radical generated by adding trifluoromethyl radical to terminal alkyne facilitates the sequential remote HAT and alkenyl migration under visible-light condition,which synthesize various trifluoromethyl substituted olefins.This reaction exhibits specific regioselectivity and wide application range.The third part presents the synthesis of vinyl trifluoromethyltthioether through radical-mediated vinyl migration strategy.Under the mild conditions,this reaction exhibited good functional group tolerance and substrates applicability.The fourth part introduces radical-mediated docking-migration strategy for alkylation of olefins.This approach of introducing alkyl and oxime into the alkenes via designed and produced dual-function reagent offers a novel method for olefinic alkylation.