Study On The Reactions Of Aryne And 1,3-Dipole

This thesis mainly consists of three parts: review of cycloaddition reactions of aryne and 1,3-dipole,studies on the reaction of aryne with 6-diazocyclohex-2-en-1-one derivatives and the reaction of aryne with Mitsunobu reagent.Chapter 1: Review of cycloaddition reaction of aryne and 1,3-dipoleIn this chapter,the background of aryne was introduced,including structure,activity and preparation methods,and the various dipolar cycloaddition reactions of aryne were summarized at the same time.Chapter 2: Study on the reaction of aryne with 6-diazocyclohex-2-en-1-one derivative.Indazole structural units exist widely in natural products and drug molecules with important biological activity,so organic chemists have developed a lot of efficient methods to construct the indazole skeleton.The 1,3-dipolar cycloaddition reactions of aryne and diazo compounds is an efficient method for the synthesis of indazoles.However,to use diazo compounds as the dipole,these accomplishments mainly dealt with open-chain diazo substrates,and there were seldom reports involving cyclic diazo compounds.In this chapter,by adjusting the substrate structure,we obtained spiro-3H-indazoles via 1,3-dipolar cycloaddition of aryne with 6-diazocyclohex-2-en-1-one derivative and a series of fused-2H-indazoles by subsequent rearrangement under the heat / acid conditions.Chapter 3: Study on the reaction of aryne with Mitsunobu reagent.Aryl hydrazine is a very important intermediate for organic synthesis,it can be used for the preparation of a series of nitrogen-containing heterocyclic compounds such as indoles,pyrazoles,indazoles and others.Besides traditional synthetic approaches,such as electrophilic amination of ary derivatives with azodicarboxylates.With the rise of transition-metals,the coupling reaction of aryl metal reagents and aryl halides catalyzed by transition-metals has become an important method for the preparation of aryl hydrazines.In this chapter,a new route to arylhydrazides involving the reaction of the 1,3-zwitterion generated in situ from the Mitsunobu reagent and aryne under mild conditions(no transition metal participation)has been developed,and further application to access diverse nitrogen-containing heterocycles in one pot.