Asymmetric Aryl-Alkenylation Of Unactivated Alkenes With Electrophiles

This paper is divided into two parts.In this manuscript,we firstly summarize the development of difunctionalization of unactivated alkenes,and then present the asymmetric aryl-alkenylation reaction of unactivated alkenes using electrophiles.Part ?: The development of difunctionalization of unactivated alkenesTransition metal catalyzed difunctionalization of unactivated alkenes has been widely used in organic synthesis.The cross-couplings coupled with the Heck reaction have emerged as an efficient approach for difunctionalization of unactivated alkene.This method can be divided into two types: intermolecular three components reaction and the cyclization/cross-coupling reaction.?-H elimination is the major problem in both reactions.Over the past years,several methods have been developed to inhibit the ?-H elimination.The reductive coupling of electrophiles has great potential in difunctionalization of unactivated alkenes.However,this process has been challenged with chemoselectivity,regioselectivity and enantioselectivity.Part ?: Asymmetric aryl-alkenylation of unactive alkenes with electrophilesThe development of new methods for asymmetric difunctionalization of unactivated alkenes is of great attractive,which has exhibited great advantages in the synthesis of complex chiral molecules.We demonstrate here an asymmetric difunctionlization reaction of unactivated alkenes with electrophile.This reaction proceeds under mild conditions,with easily accessible chiral pyrox as a ligand.A wide range of substrates were tolerated,and the products can be obtained with high enantioselectivity.The introduction of alkenyl groups will be useful to further increase molecular diversity and complexity.In addition,this reaction can be applied to construct many important chiral molecules,such as dihydrobenzofuran,dihydroindole and indamine.It also shows good applicability in late-stage modification of complex molecules,such as peptides and indomethacin.