Copper-catalyzed Cyclization And Azidation Of γ,δ-unsaturated Ketone O-benzoyl Oximes

This thesis deals with the copper-catalyzed cyclization and azidation reaction ofγ,δ-unsaturated oxime esters.It is devided into three chapters.The first chapter is a review of the recent studies on the C-N coupling reactions based on the N-O cleavage of oxime derivatives.The various methods are introduced according to the types of the reactions and catalysts used.The second and the third chapters describe my own research during the period of my graduate study.The main contents are summarized as follows.(1)The copper-catalyzed cyclization and azidation of γ,δ-unsaturated ketone O-benzoyl oximes was investigated.It was found that tetrakis(acetonitrile)copper(Ⅰ)hexa-fluorophosph could effectively promote the N-O cleavage of γ,δ-unsaturated ketone O-benzoyl oximes,thus formed imine intermediates would undergo the 5-exo cyclization,and subsequently azidation in the presence of TMSN3 to afford the corresponding dihydropyrroles.The yields of the products can be increased by using 2-cyclohexanone carboxylic acid ethyl ester as the ligand.The current reaction constitutes a new protocol for the diamination of olefins.(2)Attempt was made to realize the intermolecular C-N coupling reaction between oxime esters and terminal alkynes by using copper salts as catalyst.So far,the expected results have not been obtained.Further work is being done in our lab.