The Study On Copper-Mediated Allyl Amination And Aromatic Ortho C-H Cyanation Reaction

Allylamines and cyanides are important in organic synthesis,and the corresponding products are widely used as pharmaceutical products and synthetic intermediates.At present,transition metals such as Pd、Cu、Ru、Ir and Co have been extensively explored.Compared with other expensive transition metals,copper salt stands out because of its cheap advantages.The traditional allyl amination and cyanidation have been explored and studied by many researchers.However,it is also worth looking forward to developing more attractive responses.Thus,this thesis is divided into two types of work to investigate as follows:(1)The copper-catalyzed ring-opening reactions of cyclopropanes by N-fluorobenzenesulfonimide toward N-allylsulfonamides.As key three-carbon building blocks in organic synthesis,arylcyclopropane reacts with NFSI under the catalysis of Cu(I),proceeding with ring opening and β-H elimination.Allylamines with different substituents were obtained by this method.Although the preparation schemes of allylamine are constantly developing and seem to be diverse,this new synthesis strategies may provide additional synthesis ideas for the field of drug research.(2)The copper-mediated direct aromatic ortho-C-H cyanation by AIBN.Compared with traditional aryl halide cyanidation,aromatic C-H bond direct cyanidation has high efficiency and less waste.AIBN served as an ideal cyanation reagent in the cyanation of tertiary amines,terminal alkynes,S-cyanation of disulfides,and N-cyanation of sulfoximines.However,to date,only one example has been reported of direct cyanation of aromatic ortho-C-H bond.Here we reported an AIBN-involved,copper-promoted cyanation of heteroaromatic hydrocarbons on the ortho-C-H bond with a range of substrates including indole,pyrrole,carbazole,and thiophene.