Fe-Catalyzed Trifluoromethyl-Decarboxylation And Aldehyde Decarboxylation-Decarboxylation Series Reaction Of Two Different Olefins

Through the double functional group reaction of olefins,we can through a one-step reaction to simultaneously introduce two new atoms or groups（including carbon and heteroatom）to the both ends of the olefin C=C bonds to build two new chemical bonds.It can not only rapidly increase the diversity of product molecules,but also reduce the synthetic steps,improve the efficiency of synthesis and reduce the amount of metal reagents.In recent years,this field has developed rapidly and become the hot spot and frontier of organic synthesis chemistry research.However,there are few reports on the reaction from difunctionalization of a single olefins to the dual difunctionalization of two different olefins.In this paper,Fe-Catalyzedtrifluoromethyl-decarboxylationandaldehyde decarboxylation-decarboxylation series reaction of two different olefins are studied by using the double bonds with different electron cloud densities in combination with the dual functional group strategy of olefins.the specific content is as follows:1.We developed Fe-Catalyzed trifluoromethyl-decarboxylation reaction of two different olefins under mild conditions using sodium trifluoromethylsulfonate,allylbenzene and cinnamic acid derivatives as substrates,and synthesized a series of chain increasing olefins.In this reaction,cheap and easily obtained sodium trifluoromethyl sulfonate was used as raw material,and trifluoromethyl radicals were provided by desulfurization under the catalysis of iron.By addition of two different alkenes in order,oxidative decarboxylation of cinnamic acid was carried out at last,and C（sp³）-CF₃and C（sp³）-C（sp²）bonds were constructed in one step.In addition,we have done some research on the mechanism of the reaction and proposed that the series reaction may have experienced the reaction process of free radicals.2.We developed an iron-catalyzed alkylation of two different olefins using electron-deficient olefins,cinnamic acid derivatives and aldehydes as substrates.This reaction uses cheap and easily obtained aliphatic aldehyde to oxidize decarbonylation under the action of DTBP as free radical initiator to provide primary,secondary or tertiary alkyl radicals.By adding two different alkenes in sequence,the oxidative decarboxylation of cinnamic acid is finally carried out to obtain the alkenes with chain growth.This method can be used to construct relatively complex molecules from cheap and easily available starting materials by one-pot method,and also provides certain reference value for the selective study of free radical addition reaction.Finally,the mechanism of the three-component tandem reaction was investigated in detail,including the BHT trapping experiment and free radical locking experiment,which fundamentally confirmed that the reaction underwent free radical pathway.