Fe-Catalyzed Alkylation-azidation Cascade Reaction Of Alkenes

The olefin bifunctionalization reaction has become one of the most important research contents in the field of chemistry.It is an important mean for synthesizing many biologically active compounds and natural products,embodying modern synthesis concepts such as high-efficiency,environmental friendliness,and atomic economy,thus becoming a powerful tool for generating highly functionalized scaffolds in organic synthesis.In recent years,studies on the olefin bifunctional reaction have been reported successively,such as:diazidation,azidocyanation,trifluoromethylation-azidation,and trifluoromethylation.However,there are few related reports on alkyl-azidation of olefins at present,and this is precisely the lack of effective C(sp3)-C(sp3)type coupling method for drug synthesis.1.The aiphatic aldehydes are oxidative decarbonylated under the oxidation system of Fe(acac)2/DTBP to provide alkyl radicals to achieve the three-component olefin alkyiation-azidation cascade reaction with aromatic olefns and TMSN3,Successfully linked the oxidative decarbonylation of aliphatic aldehydes with the functional group reaction of olefins,efficiently constructed C(sp3)-C(sp3)and C(sp3)-N in one step,and synthesized diffrent chain alkylazide compounds with important application value.We then conducted a general study of olefin derivatives and fatty aldehydes.In addition,we conducted some mechanistic studies on this reaction and proposed that the tandem reaction may have undergone a reaction process of oxidizing radicals.2.C(sp3)-H bonds in simple alkanes and polychloro me thane are activated by the catalytic oxidation system of Fe(acac)2/DTBP to provide alkyl radicals for three-component tandem reaction of various types of olefin derivatives and TMSN3,effectively constructing C(sp3)-C(sp3)arnd C(sp3)-N,and selectively to synthesize a series of cyclic alkyl azide conpound and y-aziio chloro alkane compound with important application value.Finally,we carried out a detailed mechanism investigation of the three-component cascade reaction,including the TEMPO capture e)xperiment and the radical lock experiment,which fundamentally confirmed that the this reaction proceeded via radical tandem reaction.