Study On 1,3-Dipolar Cycloaddition Reaction With Involved Acetylene

1,3-Dipolar cycloaddition reaction has attracted particular attention of organic chemists because of their advantages of molecular diversity,regioselectivity,stereoselectivity and so on.The electron-deficient alkynes can react with nitrogen-containing nucleophiles to give active dipolar intermediates.Then,these active dipole intermediates can take part in 1,3-dipolar cycloaddition reaction and Diels-Alder reaction,etc.The synthetic applications of electron-deficient alkynes in organic synthesis is becoming more and more extensive field.In this paper,we investigated the formation of new 1,3-dipoles generated from the reaction of a-amino acid with electron-deficient alkynes and their 1,3-dipolar cycloaddition reactions for the synthesis of diverse functionalized fused pyrrolidine and spiropyrrolidine derivatives1.The three-component reaction of a-amino acids,dialkyl acetylenedicarboxylates and N-substituted maleimides in refluxing ethanol resulted in diverse pyrrolo[3,4-c]pyrrole derivatives.Various amino acids with different structures afforded several types of fused pyrrolidine products,which showed this three-component reaction has rich molecular diversity and high diastereoselectivity.The advantages of this reaction are broad substrates,simple raw materials,mild reaction conditions and simple manipulation,etc.This reaction provided a convenient method for synthesizing complex fused pyrrole derivatives.The structures of obtained compounds were characterized by IR,1H NMR,13C NMR,HRMS spectra and the single crystal structures of six compounds were determined by single crystal diffraction method.2.The 1,3-dipolar cycloaddition reaction of amino acids,dialkyl acetylenedicarboxylates and 2-arylidene-1,3-indanediones in ethanol was studied.This reaction afforded a series of novel functionalized of spiropyrrolidine derivatives in good yields.Totally,32 new compounds were obtained and their structures were established by IR,1H NMR,13C NMR,HRMS spectroscopy.Five single crystal structure were determined by single crystal diffraction method.3.The domino reaction of amino acid with dialkyl acetylenedicarboxylate was thoroughly investigated.In the domino reaction,dialkyl acetylenedicarboxylate not only reacted with amino acid to give 1,3-dipoles,but also react as dipolarophile to proceed 1,3-dipolar cycloaddition reaction to give poly-substituted pyrrole and pyrrolazine derivatives.Totally,13 new compounds were synthesized and their structures were identified by IR,1H NMR,13C NMR and HRMS spectra.Four single crystal structures were determined.