Research On Radical Decarbonylative Addition Of Aliphatic Aldehyde To Alkenes

Constructing new chemical bonds is the core of organic synthesis chemistry,and the key of the synthesis of human need drugs,pesticides,and various organic functional materials.In recent decades,many achievements were reported on transition metal catalyzed coupling reactions to generate new chemical bonds.But with the rising concept of "green chemistry" in recent years,the development of mild and environment friendly conditions,,the easy availability of reactants have become the focus in the current organic chemistry research.This dissertation focused on environmentally friendly decarbonylation reactions to construct new chemical bonds,to realize the decarbonylative nucleophilic-addition of alkyl radical to electron-deficient alkenes,and a three-component decarbonylative alkylation-aminoxidation of styrene derivatives with aliphatic aldehydes and N-hydroxyphthalimide(NHPI)to yield phthalimide protected alkoxyamines.1.A metal-free decarbonylative addition of aliphatic aldehydes to electron-deficient aliphatic alkenes has been developed.The reaction takes tertiary butyl peroxide as a free radical initiator and oxidant to induce homolytic cleavage of aldehyde C(sp2)-H bond.After turned to be an acyl radical,losing an molecular of CO to produce a alkyl radical,which adds to the electron-deficient olefins to generate a new carbon-carbon bond and obtain decarbonylative-addition adduct.The reaction expands the scope of the aldehyde's radical type decarbonylation reaction,at the same time,it has good tolerance for both linear and branched aldehydes.2.A convenient metal-free decarbonylative alkylation-aminoxidation of styrene derivatives with aliphatic aldehydes and N-hydroxyphthalimide(NHPI)to yield phthalimide protected alkoxyamines is developed.Also with DTBP as an oxidant and radical-initiator,this reaction smoothly converts aliphatic aldehydes intoalkyl radicals and subsequently allows for the cascade construction of C(sp3)-C(sp3)and C(sp3)-O bonds via radical-radical coupling.