Copper-Catalyzed Intermolecular Aminobromination Of Olefins:Synthesis Of Vicinal Bromamine Derivatives

The vicinal haloamines are important class of organic synthesis intermediates,they are also important structural fragments of drug active molecules.Therefore,the development of simple and efficient methods for the synthesis of the vicinal haloamines is one of the important tasks of organic synthetic chemists.In the past few decades,various methods for synthesizing the vicinal haloamines have been developed,including aminohalogenation of olefins,aminohalogenation of alkynes and ring opening of vinyl aziridines.Among them,catalyzed aminohalogenation of olefins is one of the most straightforward and effective methods for the synthesis of the vicinal haloamines,such as transition metals V,Mn,Fe,Ni,Cu,Pd,Ag,etc,as well as by non-metallic catalysts which include use of bronsted acids such as H₂SO₄ or ionic liquid media[Bmim][BF₄].Recent years,catalyzed asymmetric aminohalogenation of olefin has achieved great success.However,at present,most of the aminohalogenation of olefins are driven by intramolecular nitrogen cyclization,or the N-X compounds act as both nitrogen sources and halogen sources,which greatly limit the further application of aminohalogenation of olefins.In addition,through research literature,we found that copper-catalyzed radical-based intermolecular aminohalogenation of olefins has rarely been reported.Therefore,the development of an intermolecular aminobromination reaction of simple olefins with independent nitrogen and bromine sources is of great importance.In this thesis,using cheap and readily available styrene derivatives as the substrates,N-fluoroarylsulfonimides?NFSI?as the nitrogen source and lithium bromide as bromine source under mild conditions,we realized copper-catalyzed nitrogen-centred radical initiated intermolecular aminobromination of olefins and synthesized a series of the vicinal haloamines with exclusive regioselectivity.It provides a new way to the synthesis of the vicinal haloamines.