Nickel-Catalyzed Migratory Hydroacylation,Remote Hydroamination,and Asymmetric Carboamination Of Olefins

Alkenes are versatile and readily available starting materials for many types of transformations,including hydrogenation,hydrofunctionalization,and difunctionalization.Metal-hydride catalyzed olefin functionalization can quickly introduce a series of functional groups and has attracted attention of many chemists.But most of the traditional hydrofunctionalization occurs at the original position of C=C double bonds.Instead,the recently emerged metal-hydride catalyzed remote functionalization of alkenes could introduce a functional group into the distal and challenging position.Based on the existing research results of our group,my doctoral dissertation is focused on the nickel-catalyzed remote hydroacylation,remote hydroamination,and asymmetric 1,2-carboamination of alkenes.In the first part,we have developed a Ni H-catalyzed migratory acylation of alkyl halides or alkenes with alkyl carboxylic acids.In this strategy,we used two abundant starting materials,alkyl bromides and carboxylic acids,allows the direct acylation of the benzylic C(sp3)-H bond with high yield as a single regioisomer.As an alternative,the alkyl bromide could be replaced by the proposed olefin intermediate and commercially available ~nPr Br to achieve a remote hydroacylation process.In the second part,we have developed a Ni H-catalyzed remote hydroamination of olefins or alkyl halides with O-Benzoylhydroxylamines.With this strategy,linear amines could be obtained with better yields and higher regioselectivity from internal olefins.At the same time,we determined the rate-determining step of the reaction and the role of additives in the reaction process through preliminary mechanism experiments.In the third part,we have developed a nickel-catalyzed asymmetric reductive 1,2-carboamination of alkenes.This mild,modular,and practical protocol provides rapid access to a variety of?-chiral amines with an enantioenriched aryl-substituted quaternary carbon center in good yield and with excellent enantioselectivity.Finally,we proposed the possible reaction mechanism through a series of mechanism experiments.