Research Of Copper Catalyzed Trifluoromethylation-alkenylation Recation Of Olefins

The introduction of different functional groups through the difunctionalization of alkenes is one of the hottest strategies in organic synthesis,which enables the one-step construction of two adjacent carbon carbon or carbon heteroatom bonds from simple substrates,significantly improving the structural diversity of molecules,as well as providing good atom economy and efficiency,and therefore,the field has received considerable attention in recent decades.On the other hand,due to the stable chemical properties of CF3 and its excellent solubility in nonpolar solvents,the trifluoromethyl group has special biological activity and thereby occupies an indispensable part in the field of human medicine and pesticides.The introduction of CF3 into organic compounds can significantly improve their physicochemical properties and exert distinct modifications on the target compounds,which attracted great interest in the synthesis of trifluoromethylated products.Thus,developing synthetic methods for the rapid construction of trifluoromethyl containing compounds becomes one of the hottest areas in organic synthesis.In this paper,we aim to synthesis of a series of trifluoromethyl containing compounds using copper catalyzed olefin trifluoromethylation alkenylation reactions starting from alkenes,togni-i reagents,and alkenyl,arylboronic acids.The specific research content is as follows:Firstly,through the selection of reaction conditions such as ligands,solvent,substrate ratio and etc.,we accomplished a tandem reaction of olefins,trifluoromethyl reagent togni1 and aryl allylboronic acids.Under the regulation of ligand effect,the reaction can effectively reduce the generation of by-products,presenting the target products in 52%99%yields.And,based on the related literature reports,we speculated on the possible mechanism and tentatively performed an attempt for the asymmetric catalytic reaction.Secondly,based on the above work,we wish to enquire routes for the rapid construction of homocycles through this type of reaction.After a preliminary screening,using 1,5-cyclooctadiene as the substrate,copper in tandem with a dioxazoline ligand as the catalytic system,and alkenyl boronic acid as well as togni-1 reagent trimers,the reaction underwent a one-step single electron migration and rearrangement to finally yield cyclophilic compounds,which were investigated and found to exhibit substrate suitability that could be extended to arylboronic acids.In summary,we developed a new strategy for the rapid construction of cyclophilic compounds using specific dienes as substrates with low yields of reaction byproducts and high diastereoselectivity.This work is devoted to the development of a novel alkene difunctionalization strategy using nonactivated alkenes as substrates,enabling such alkenes to complete transformations under mild reaction conditions.And the introduction of an additional alkenyl group along with the introduction of a trifluoromethyl group provides possibilities for further functionalization and also important intermediates for the synthesis of biologically active fluorous drugs.