Copper-catalyzed Asymmetric Electrophilic Reaction Of ?-naphthol And ?-naphtholamide

At present,transition metal catalysis has been widely used in organic synthesis,medicine and material synthesis.Benefiting from the rich electronic properties and the large deformable electron cloud.Therefore,transition metals be used for catalysts in the reaction has played a very important role in the construction of new chemical bonds.On the other hand,the azide group is a type of very valuable synthetic building block,which exists widely in many natural active substances and medicines and the azide group is also considered to become effective precursors of nitrogen guests and nitrogen ions.Therefore,scientists have been concerned about how to efficiently construct asymmetric organic azides.There have been many reports on the construction of chiral azide compounds using asymmetric transition metals as catalysts,but most of them are nucleophilic reactions with very few electrophilic reactions.Therefore,there is a very important practical significance that the development of new asymmetric electrophilic reactions to expand new fields and synthesize new chiral azides..Based on the previous work and combined with the previous work of our research group,this paper uses Cu as catalysts to develop a new asymmetric electrophilic dearomatization reaction to construct a series of new chiral azide compound.The content is as follows:2-hydroxy-N,N-dibenzyl-1-naphthyl carboxamide and T-shaped iodine?III?azide are used as template substrates,10 mol%Cu?CH₃CN?₄PF₆ is used as a catalyst,and 12 mol%dbfox/Ph is used as a ligand.The chiral azide compound containing quaternary carbon center was obtained at room temperature in 86%yield with 95%ee using CH₂Cl₂ as a solvent.At the same time,the scope of substrate applicability of this method is further investigated.The target product can be obtained with high yield and high enantioselectivity for different substituents and different amide groups on the naphthalene ring.Combined with the experimental results and deduced through the mechanism,it is finally proved that metal Cu and dbfox/Ph ligand as chiral catalyst and the iodide azide cracking produces an azide ion for the electrophilic reaction.In summary,this article is the first enantioselective copper-catalyzed electrophilic azidation of?-naphthol?-naphthamide.The use of simple and mild reaction conditions to generate chiral azides with high yields and high ee.The new method of synthesizing chiral azide has very important positive significance for the synthesis of chiral azide.