Free Radical-mediated C-C Bond Functionalization

The C-C bonds is the basis skeleton of organic molecules.The functionalization of C-C bonds is an important approach for molecular skeleton modification.Currently,the selective functionalization of C-C bonds for molecular skeleton is challenging.The free radical-mediated selective cleavage of the C-C bond of cyclobutanol,can be applied for rapidly constructing ?-functionalized ketones.This enables site-specific introduction of functional groups into the molecular skeleton.In addition,intramolecular functional groups migration through the radical-mediated difunctionalization of unactivated olefins is an effective way to achieve functionalization of distal C-C bonds.The novel and efficient strategy gives unique regioselectivity.The approaches for the functionalization of C-C bonds will be investigated detailedly in this thesis.This thesis mainly includes the following four parts:In part one,the relative literatures about transition-metals or free radicals-mediated cleavage of C-C bonds and functional groups migration to achieve functionalization of C-C bonds were summarized.Additionally,the basis and significance of my project were introduced in this part.In part two,manganese-catalyzed ring-opening of cyclobutanol via free-radical mediated C-C bond cleavage was introduced.The thioether compounds were rapidly and efficiently constructed when Mn(OAc)3.2H2 O was used as a catalyst,Bipy as a ligand,BI-OH as an oxidant,and Ph SSPh as a radical scavenger.The mild reaction exhibits broad scopes and excellent functional group compatibility.In part three,the work on the functionalization of remote C-C bonds via the addition of azide radicals and the cyano migration strategy was described.Azide radicals produced by the oxidation of TMSN3 were added to olefins.The cyano migration strategy provides an efficient way to synthesize the cyano azide products via the cyclic transition state.In part four,the work on the functionalization of remote C-C bonds via the addition of trifluoromethyl radicals and the heteroaryl migration strategy was described.Perfluorinated alkyl radicals produced by the oxidation of Cm F2m+1SO2Na were added to olefins.Theheteroaryl migration strategy provides an efficient way to synthesize the perfluoroalkyl heteroarylation products via the cyclic transition state.