Thiocarbamate-Directed Cp*Co(?)Catalyzed Ortho-C-H Amination Of Phenol

O-aminophenol is a synthetic intermediate for many natural compounds,scientific materials,and pharmaceutical molecules.Especially the application in the field of medicine has attracted much attention.However,the traditional preparation method has complicated reaction steps,poor selectivity and low yields.With the development of organometallic chemistry,direct group-assisted the transition metal-catalyzed C-H bond amination reaction provides a new method for the synthesis of o-aminophenol compounds.Compared with traditional methods,this method avoids the pre-activation of carbon-hydrogen bonds,the reaction steps are simple,higher selectivity and atomic economy.In this thesis,the construction of C-N bonds to synthesize a series of o-aminophenols based on thiocarbamate-directed the Cp*Co???catalyzed C-H bond activation was studied.The main results are as follows:Hence,a simple and efficient thiocarbamate-directed the Cp*Co???catalyzed C-H bond amination reaction was developed to synthesize a series of o-aminophenol compounds.The method uses 5 mol%Cp*Co?CO?I₂ as catalyst,10 mol%Ag NTf₂,and 20 mol%pivalic acid as additive,1,2-dichloroethane as solvent,and phenyl-dimethylcarbamatester compounds and dioxazolone derivatives undergo C-H bond direct amination reaction,and 37 kinds of o-?2-benzoylaminophenyl?dimethylcarbamate are synthesized with good yields.The reaction conditions are simple and efficient,atomic economy,high selectivity,good in substrate applicability,strong tolerance of functional groups,and easy to remove the product-directed groups.According to relevant literature reports and experimental investigations,the possible mechanism of the reaction was speculated.???Scheme 1...