Fe-Catalyzed Acylation Or Alkylation-peroxidation Cascade Reaction Of Alkenes With Aldehydes

Organic peroxides are a class of compounds containing an O-O structure in the molecule.Peroxides can be used not only as oxidizing agents,but also as initiators for radical reactions.The peroxy entity can be widely found in natural products and drug molecules,and can be easily converted into functional groups such as carbonyl,hydroxy and epoxy in organic synthesis.In recent years,the direct difunctionalization of alkenes has become a powerful strategy in organic synthesis,which has also been applied to the preparation of peroxides.Although trifluoromethylation-peroxidation,acylation-peroxidation and other,s have been realized,but reports on the alkylative peroxidation of alkenes are rare,especially for the installation of an un-functionalized alkyl group.In this disertation,the iron-catalyzed alkyl-peroxidation of olefins and the acyl-peroxidation-elimination reaction of two different olefins were studied in combination with the difunctionalization strategy of olefins and the synthesis and conversion of peroxides.The details are as follows:1.We have developed a convenient Fe-catalyzed alkylation-peroxidation of styrene derivatives with aliphatic aldehydes and TBHP under mild conditions to provide chain elongated aliphatic peroxides and alkylated ketones via a one-pot procedure in the presence of DBU.With TBHP playing a triple role of a radical initiator,terminal oxidant and radical coupling partner,readily available aliphatic aldehydes were decarbonylated into 1°,2°and 3°alkyl radicals,addition to an alkene,would provide the benzyl radical,which undergoes radical-radical coupling with the ~tBuOO·to construct C(sp~3)-C(sp~3)and C(sp~3)-O bonds in one step.2.We have developed an iron-catalyzed acyl-peroxidation-elimination reaction of two olefins using electron-deficient olefins,styrene derivatives,aldehydes and TBHP as substrates,using two double bonds with different electron cloud densities.A?,?-functionalized ketone was synthesized.The reaction uses aldehyde as the source of acyl radicals,sequential addition of two different olefins,and finally coupling with a ~tBuOO·to give the corresponding peroxide.The Kornblum-DeLaMare rearrangement of the peroxide in the presence of base gives?,?-functionalized ketone.The method starts from the cheap and easily available starting materials,and can construct relatively complex molecules in one pot method,and also provides some reference value for the selective study of radical addition reaction.