Study on Copper-Catalyzed Asymmetric Hydroallylation of Unsaturated Hydrocarbons

Author:Xu Guo Xing

Supervisor:zhang qian xiong tao


Degree Year:2018





Asymmetric catalysis plays a very important role in the total synthesis of natural products and the synthesis of drugs currently.The asymmetric allylic substitution has been received extensive attention in recent years,because a newly generated chiral center can be constructed while a olefin fragments also can be introduced.In this paper,we used the cheap and low toxic copper salt as catalyst,organic copper compounds prepared in situ by the addtion of Cu-H compounds to unsaturated hydrocarbons could be coupled with allylic electrophilic reagents.Compared with the traditional coupling between organometallic reagents and organic electrophilic materials,this method accorded with step economy,excellent functional compatibility,and avoided the production of metal waste.Unsaturated hydrocarbons as latent carbon nucleophile has more significant advantage undoubtedly.The research content mainly includes the following two aspects.1.Alkyne is an important commodity for petrochemical and coal chemical industry,how to achieve efficient conversion of alkynes has extremely important theoretical and practical significance.We used alkynes as an latent nucleophilie coupling with allylic electrophilic reagents,a series of chiral branched type and the linear 1,4-diene derivatives could be synthesised via ligand-controlled regiodivergent and enantioselective hydroallylation of alkynes.2.Based on the allene has the characteristics of unique structure and high reactivity,many reaction sites and rich reactive type,we achieved the asymmetric allyl-allyl coupling reaction with allylic electrophilic reagents using allene as an latent allylic nucleophilic reagents instead of allylcopper compounds,.A series of 1,5-diene compounds with high enantioselectivity and high regioselectivity have been synthesized,including the 1,5-diene compounds containing the quaternary carbon stereo center.