Nickel-catalyzed Boration And Rearrangement Reaction Of Homoallyl Carbonates

Allyl reagents are an important class of building blocks,which are widely used in the synthesis of unsaturated hydrocarbon compounds.Among them,allylboronates and allyl carbonates are of considerable interest to synthetic chemists due to their diverse reactivity and functional group tolerance.Allylboronates can not only undergo nucleophilic addition reactions with aldehydes,ketones and imines to prepare homoallyl alcohols and homoallyl amines,but also participate in transition metal-catalyzed coupling reactions to achieve the introduction of allyl functional groups.Therefore,how to prepare a variety of allylboronates more efficiently and conveniently has become a very meaningful task.Ester groups are good leaving groups.Allyl ester compounds show good chemo-and stereoselectivity in the construction of carbon-boron and carbon-carbon bonds.In recent years,the transition metal catalyzed allyl ester rearrangement,which converts one allyl ester into another new allyl ester,has gradually attracted the research interest of chemists.This paper is divided into three chapters:（1）The conversion and synthesis of allyl boride and the rearrangement reaction of allyl carbonate were outlined.This paper mainly focuses on the research progress of the nucleophilic addition reaction of allyl borides to different aldehydes,ketones and imines,the coupling reaction of allyl borides,the synthesis reaction of allyl borides catalyzed by different transition metals and the rearrangement reaction of allyl esters catalyzed.（2）A new synthesis of arylated endo-arylallyl boronates was developed with Ni（cod）₂ as catalyst.Under the optimized reaction conditions,a series of allylboronate products were obtained in moderate to good yields with high selectivity under room temperature conditions.The reaction has a wide substrate scope and many functional groups are well tolerated.The resultingγ-arylallyl boronates are expected to play an important role in more biosynthesis versus modification.（3）The conversion ofα-arylhomoallyl carbonates toγ-arylallyl carbonates was achieved with Ni（OTf）₂ as catalyst.Through the optimization of reaction conditions and the preliminary exploration of substrate scope,the synthesis method of allyl carbonate was expanded and the conversion application of high allyl carbonate was enriched.