| As the important application of N atoms in pesticide,medicine and materials,the construction of C-N bond is a hot research area.Recent years,metal catalytic C-H amination is the most popular way in building C-N bonds,it overcomes the drawbacks in traditional functional transformation such as poor atom economy.Numerous synthetic methods have been developed for the construction of amidyl C-N bonds.The most common route for the synthesis of amide is the pre-activation of carboxylic acid moiety then reacting with amine.The amine activation method has been rarely reported so far.This paper first summarizes the numerous methods used for the synthesis of amide from two aspects:pre-activation of carboxylic acid moiety and pre-activation of amino moiety.Then this paper summarizes the C-H amination catalyzed by different metal.By comparing,we found that the N activation strategy was widely used at the reaction of aryl C-H amination and pre-activation of amino moiety for the construction of amidyl C-N bonds,but the two process were independent.The methods of metal catalytic C-H amination and the methods of pre-activation of amino moiety for the construction of amide applied together for the efficiently formation of C-N bonds has not been reported.First of all,an Ir(Ⅲ)-catalyzed one-pot or stepwise synthesis of N-phenylcarboxamides via C-H sulfonamidation following carboxamide bond formation enabling three-component sequences of benzamides,bifunctional nitrogen source:trichloroethoxysulfonyl azide(TcesN3),and metal carboxylates is disclosed.In this reaction,no oxidants or coupling reagents are needed and acylating agents are all stable and commercially available.So,this method provides a new strategy for the construction of acyl C-N bond and amidyl C-N bond together.The functional-group tolerance of the reaction is good,the stable carboxylates including primary,secondary and tertiary alkyl,alkenyl and phenyl carboxylates.Also,this method can be used for the late-stage derivatization of complex natural products and bioactive substances. |
