Studies On The Debenzylative Sulfonylation And Acylation Of N-benzyl Tertiary Amines

This thesis has three chapters: The first chapter is a literature review,which mainly discusses the research progress of the C-N bond cleavage reaction of tertiary amines.The other two chapters introduce the debenzylative sulfonylation and acylation of Nbenzyl tertiary amine in detail.Chapter 1.Research progress on C-N bond cleavage reaction of tertiary aminesTertiary amines are widely found in nature and are commonly more stable than primary and secondary amines.However,the electron-rich C-N bond has a high dissociation energy,which makes tertiary unsuitable as a raw material in organic synthesis.Therefore,the activation of the tertiary amine C-N bond has become a hot research topic in organic synthetic chemistry.This chapter summarizes five methods to activate C-N bonds in tertiary amines,i.e.,the formation of quaternary ammonium salts,N-oxides,aminoalkyl radicals,ionic intermediates and charge-transfer complexes.Chapter 2.Study on the debenzylative sulfonylation of tertiary benzylaminesThis chapter provides a strategy of visible light-promoted debenzylative sulfonylation reaction of tertiary benzylamines.This method has the advantages of economy,high efficiency and wide applicability.Compared with traditional methods,this synthetic strategy does not require the use of metal catalysts,additional oxidants or organic ligands,and can selectively achieve the cleavage of benzylic C-N bonds.Chapter 3.Study on the debenzylative acylation of N-benzyl tertiary amineThis chapter studies the debenzylative acylation reactions of tertiary Nbenzylamines with chloroformate compounds and aryl chlorides.Carbamates are effective ingredients in pesticides,and are commonly prepared from highly toxic phosgene.To avoids the use of toxic phosgene,we here provide a one-step debenzylative coupling reaction of tertiary N-benzylamines with chloroformate/aryl chloride,which are performed under mild conditions without removing the benzyl group beforehand,to yield carbamates or amides.