Study On Cobalt Catalyzed Reaction Of Iododifluoromethyl Ketones With Alkynes/ Alkenes

Fluorinated organic compounds have been widely used in the fields of pesticide,medicine and materials because of their unique physical and chemical properties.So how to efficiently introduce fluorine atoms or fluorine groups into organic molecules has attracted a lot of attention in academic.The bifunctional reaction can economically and effectively introduce two different groups or atoms to the two ends of the unsaturated hydrocarbon in one step,which reduces the synthesis steps,reduces the cost and provides more methods for the construction of the diversity of chemical structure.In recent years,transition metal catalyzed bifunctional reaction is in the ascendence.This paper focuses on the synthesis of α,α-difluorone compound and attempts to introduce the cobalt catalytic reaction system into the unsaturated hydrocarbon bifunctional group reaction to expand a new way of reaction.The mechanism of free radical circulation in cobalt catalyzed fluoroalkylation reaction was demonstrated by mechanism study,which deepened our reunderstanding of cobalt catalysis.The main content of the paper is as follows:一、Study on the free radical addition reaction of α-iodine-α,α-difluoromethyl ketone block with alkynes under the cobalt catalyst.In this chapter,we take α-iodine-α,α-difluoromethyl acetophenone and phenylacetylene as template reactions,and carry out a series of conditions screening for catalyst,ligand and solvents to determine the optimal conditions.Under the optimal conditions,the structure of the reaction substrate is expanded,and finally E-type olefin α,α-difluoromethyl acetophenone compounds are obtained with high stereoselectivity.二、Study on the free radical addition reaction of α-iodine-α,α-difluoromethyl ketone block with alkenes under the cobalt catalyst.In this chapter,under the optimal conditions of the reaction between α-iodine-α,α-difluoromethyl ketone block and alkynes,the substrate of this reaction was extended to olefin by adjusting the amount of zinc powder,and a series of alkanesα,α-difluoromethyl ketone compounds were obtained.In addition,the reaction was successfully applied to the structural modification of magnolol,which is a natural product.