KMnO₄-Mediated Oxidative C-N Bond Cleavage Of Tertiary Amines

As an important carrier of biochemical processes,nitrogen-containing compounds are widely found in various living organisms in nature.Chemical transformation based on the C-N bond cleavage often simplifies complex reactions,which also be used to modify certain specific molecules.However,the C-N bond cleavage of tertiary amines requires higher energy,which makes it desirable to resort to simple and efficient C-N bond cleavage,achieve its directional transformation,which is challenging in the field of chemical research.Especially based on the C-N bond cleavage,the highly efficient new atomic economy reaction is one of the important research directions of organic synthetic chemistry in the 21st century.Tertiary amines are relatively stable chemical properties and inexpensive to be obtained.In recent years,the cross-coupling reaction of tertiary amine with other substrates by C-N bond cleavage has attracted attention of chemists.In the paper,C-N bond cleavage of tertiary amine were studied in depth.This thesis consists of three parts,the main contents were as follows:Chapter 1 Research Progress on C-N Bond Cleavage of Tertiary AminesThe research progress of C-N bond cleavage of tertiary amines was reviewed.The methods of the C-N bond cleavage of tertiary amines could be divided into two broad categories:Transition metal catalyzed C-N bond cleavage of tertiary amines.The C-N bond cleavage by insertion of transition metal,many new reactions were produced in combination with the classical coupling reaction.Through these new reactions,important molecules such as biaryl,quinazinone,pyrazole,isoquinoline,quinolinone,amine and amide were effectively prepared.Metal-free catalyzed C-N bond cleavage of tertiary amines,such as iodine/peroxide,or strong base,or photoelectric conditions etc.These methods were simple to operate,mild condition,and more importantly,metal ion residues were avoided.Although there has been great progress about C-N bond cleavage of tertiary amines,there are still many problems.We are committed to researching efficient,simple new methods for the C-N bond cleavage of tertiary amines,especially to improve atom utilization and reduce costs of reaction.Chapter 2 KMnO₄-Mediated Oxidative C-N Bond Cleavage of Tertiary Amines—Synthesis of AmidesThe reaction of KMnO₄ mediated C-N bond cleavage of tertiary amine was first introduced.After the alkyl carbon bonded to the nitrogen was oxidized to carboxyl group,it was decarboxylated to form secondary amine under basic conditions.The secondary amines reacted with acyl chloride to generate a series of tertiary amides in moderate to good yields.The advantages of method was mild conditions,simple and convenient operation,and good functional group tolerance.The target products were characterized by ¹H NMR,¹³C NMR,HRMS.Chapter 3 KMnO₄-Mediated Oxidative C-N Bond Cleavage of Tertiary Amines—Synthesis of SulfonamidesA simple and effective oxidation process has been developed to achieve selective C-N bond cleavage of tertiary amines.Under the reaction system,secondary amines were produced by C-N bond cleavage of tertiary amines with KMnO₄ oxidized,which reacted with sulfonyl chloride to generate a series of sulfonamides.The target products were characterized by ¹H NMR,¹³C NMR,HRMS.