Nickel-catalyzed Remote Hydroalkylation And Remote Hydroamination Of Olefins

Despite encouraging progress has been made in the research area of C-H activation over the past two decades,the selective functionalization of sp3 C-H bonds remains a challenge for synthetic chemists.At present,most strategies need a polar directing group nearby to ensure good reactivity and regioselectivity.This strategy reduces its utility in synthesis.Therefore,non-directed C-H functionalization is more attractive for organic synthesis.Olefin is readily available and easily prepared.Compared to inert sp3 C-H bonds,C=C double bonds are more reactive and can readily hydrofunctionalization or difunctionalization.Over the past two decades,olefin hydrofunctionalization mediated by metal hydride has attracted the attention of chemists.However,there have been relatively few reports on the development of remote functional groups using olefins and metal hydride.This strategy avoids the complex operation of introducing/removing a directing group from the substrate,which reduces the utility and practicality in organic synthesis.This thesis is focused on the functionalization of remote C-H bonds via the strategy of nickel-catalyzed olefin isomerization-cross coupling reactions.It mainly includes the following three parts:The first chapter,we introduce the background of NiH chemistry.Including development,preparation methods and applications in coupling reactions.In the second chapter,we developed a nickel-catalyzed olefin isomerization-hydroalkylation reaction with benzylic selectivity.It proceeds through olefin isomerization mediated by the in situ generated nickel hydride.Then,the benzylnickel intermediate readily undergoes oxidation addition/reductive elimination with alkyl iodides to deliver the final product.In the third chapter,we developed a nickel-catalyzed olefin isomerization hydroamination reaction to achieve the remote hydroamination of olefins.Similarly,it proceeds through olefin isomerization mediated by the in situ generated nickel hydride.Then,the less steric hindered terminal alkyl nickel species react with nitro(hetero)arenes to provide the final hydroamination product.