Study On The Conversion Of Organoammonium Salt Via Carbon-Nitrogen Bond Cleavage

Organic amines are widely found in nature,and it is also one of the most basic chemical raw materials.In the field of organic synthesis,Organic amines via cleavage of C–N bond can synthesis of various fine chemical products.However,the C–N bond of organic amines are relatively inert,its efficient activation and transformation often require harsh conditions,which also limits its transformation and application to a certain extent.Organoammonium salts are a class of compound prepared by salt forming reaction of organic amines,which has stable chemical properties.The organoammonium salts C–N bond polarity are enhanced after salt formation,and the C–N bond are easy to break under transition metal or alkaline conditions,thus carrying out various conversions.At present,the efficient conversion of organoammonium salts has shown wide application value in the synthesis of important compounds such as biphenyl,diarylmethanes,aryl ketones and aromatic internal alkynes,as well as in the construction of C heteroatomic bonds.However,the reaction research of organoammonium salts still needs to be further developed:such as the reaction of organoammonium salts with other biomass,and the transition metal-free reaction of construct aryl C–heteroatomic bond,this can enrich the activation and conversion application of organoammonium salts in the field of organic synthesis.Based on this,the paper mainly explores the palladium-catalysed deaminative/decarboxylative corss-coupling of organoammonium salts with carboxylic acids,and the transition-metal free regioselective aromatic phosphorylation and etherification of benzylic ammonium salts.The specific research contents and results are as follows:1.Palladium-catalyseddeaminative/decarboxylativecorss-couplingof organoammonium salts with carboxylic acids:Under the reaction conditions of Pd（OAc）₂as catalyst,DPPB as ligand and KO^tBu as base,the deaminative and decarboxylative corss-coupling reaction of organoammonium salts with various carboxylic acids（polyfluoroaryl carboxylic acids,propiolic acids and benzyl carboxylic acids）to synthesize a wide variety of diarylmethane and arylendyne compounds.The reaction does not require the prepreparation of the carboxylic acid salts,and the reaction conditions are simple,functional groups have a wide range of applications.In addition,the gram-scale amplification experiment and the one-pot synthesis of benzylamine as a reactant were also successfully demonstrated practical value.2.Transition-metal free regioselective aromatic phosphorylation and etherification of benzylic ammonium salts:With the promotion of KOMe and KO^tBu,benzyl ammonium salts selectively reactions with nucleophile through the benzyl cation resonant formed by the C–N bond break to produce a series of aromatic phosphorus and aromatic ether compounds.Under mild reaction conditions,all kinds of naphthalene methyl,heterocyclic methyl organoammonium salts and organic phosphine reagents and alcohol reagents can be efficiently converted into target products.The reaction can be carried out the gram scale amplification experiment and the preparation of naphthalene from simple amine,realizing the application value in organic synthesis.