Tin-mediated Preparation Of Allylic ?-acylhydrazino Esters And Allylic ?-(N-aryl)Amino Esters

Glyoxalic acid ester is a kind of organic compounds that contains carbonyl and ester functional group in a molecular.It not only possesses the advantages of simple structure,but also there are multiple reaction sites in it because of two different functional groups at the same time,which make it react with a variety of organic compounds to form intermediates and used as bulding blocks with structural diversity in organic synthsis.Therefore,glyoxylic acid ester and its derivatives can be either used to synthesize biologically active compunds in the industrial synthesis for pharmaceuticals,dyes and spices,or a good ligand and intermediate in organic synthetic chemistry.Hence,glyoxalic acid ester has a pivotal position in industrial production and in organic synthesis.Unsaturated amino acids are one of natural occurring substances with many bioactive activities.Among them,?,?-unsaturated amino acids are specially paid more attention.Because these compounds are very important protein amino acids,and often treated as precursors for the synthesis of complex amino acids and peptides.What's more,N-substituted amino acids have been widly used in biochemistry,medical science and organic synthesis.Especially many of the N-amino acids directly involved in the biological process,which show the important biological functions.So developing new methods for the synthesis of unsaturated amino acids shows theoretical significance and application value.This thesis includes three parts:Chapter 1:The research progress on glyoxalic acid esters in organic synthesis.This chapter briefly introduces the preparation methods of glyoxalic acid ester compounds and applications in organic synthesis process as well as their significance of industrial production.Chapter 2: Tin-mediated preparation of allylic ?-acylhydrazino esters.An one-pot reaction of glyoxylate ethyl ester,acylhydrazines and allyl bromide promoted by tin powder has been developed in this chapter.The reaction has been investigated using different acylhydrazines leading to allylic ?-acylhydrazino esters in very high yield.When allyl bromide was replaced with prenyl bromide or crotyl bromide to perform the reaction,the ?-addition products were obtained.The reaction provides a new approach for the synthesis of allylic ?–acylhydrazino esters.Chapter 3: Tin-mediated synthesis of allylic ?-(N-aryl)amino esters.In this chapter,tin-mediated “one-pot” reactions for the synthesis of allylic?-(N-aryl)amino esters from glyoxylate ethyl ester,aromatic amines and allyl bromide were explored.The process is a direct four-component reaction wihout any catalysts used and donot need to synthesize organotin reagents in advance.It has features with simple operation,mild reaction conditions and good to excellent yields.