Synthesis Of Allyl Azides And Cyclopropanes Through Transition-Metal(Fe/Au)Catalyzed Reactions Of Allenamides

Allenamides is a special kind of nitrogen-containing allene compound,which has relatively unstable and plasticity,and is a kind of widely used organic precursor.Due to the influence of the lone pair electron of the nitrogen atom on olefins,it exhibits different chemical properties from allenes,and has been studied by many scholars.Most of the derivatives constructed through carbon-carbon bonds,carbon-halogen bonds,special functional groups,etc.,exhibit physiological activities,and at the same time provide a wealth of ideas for the research of dialenamine.Based on the previous studies on transition metal catalyzed cyclization,cycloaddition and series connection of diene amines,this paper studies the intermolecular azide and[2+1]cyclization of diene amines by means of transition metal(Fe,Au)catalysis.The first part of the work:We use cheap iron(II)metal to catalyze the reaction between dienamine and azidotrimethylsilane(TMSN₃)to efficiently synthesize a series of new economically beneficial allyl azide compounds.This process has a highly regionalized stereoselectivity and can provide(E)-allyl azides in good to excellent yields.Due to the versatility of the azide group,these products can be transformed in situ to allyl triazoles and allyl amines,facilitating numerous subsequent chemical modifications.The second part of the work:On the basis of previous studies on sulfur ylide,we used gold to catalyze the reaction of allenamine and?-carbonyl sulfide ylide to synthesize a series of three-membered ring derivatives with three-dimensional configuration and containing dicarbonyl groups.The key to this reaction is that the gold catalyst acts as a Lewis acid to activate theenamine to form a gold-substituted?,?-unsaturated imine cation,which undergoes nucleophilic addition with?-carbonylsulfur ylide,and finally forms a three-membered ring compound.