Research On The Reactivity Of Copper-mediated Amidation/Electrophilic Imination Of Alkenylzirconocenes

Nitrogen-substituted olefinic compounds include three categories, such as Enamine,Enimine and Enamide. The electron-donating ability of nitrogen strongly polarizes the doublebond, which allows for an exceptionally high level of reactivity together with a strongdifferentiation of the two sp2carbon atoms. This kind compound represent the most importantclass of olefinic compounds, which has a very important influence in organic syntheticchemistry. So buliding a new, simple and efficient synthetic method of this kind compound isvery significative. In the past decades, early transition metals, especially zirconium, played amore and more important role in the new metal-organic chemical synthesis catalyzed areas,the coupling reactions of neutral organozirconates and alkynes can offer thealkenylzirconocenes and the series of subsequent reactions are mature. Besides,alkenylzirconocenes is stringent to the environment, but the yield is very high, and it can beprepared in situ to use, which can fulfill the one-pot multistep reaction from simple smallmolecules to complex compounds. So the dissertation mainly centred on the reactions ofalkenylzirconocenes and non-classical nitrogen reagents (as the electrophiles), studied thedifferent reactivity of alkenylzirconocenes by using different electrophiles containing thenitrogen, built the new ways to synthesis the imides, enimines and enamides. Three parts areincluded which are followed:Part I, The important role of nitrogen-substituted olefinic compounds in organic syntheticchemistry was reviewed. The previous synthetic method of nitrogen-substituted olefiniccompounds was introduced, especially for the method of non-classical positive nitrogenreagents and alkyl or aryl metal reagents; then, the category and research of theorganozirconates were described, especially for the neutral organozirconates.Part II, When non-classical positive nitrogen reagents such as O-benzoyloximes wereused as the electrophiles, in the present of equivalent copper chloride, it can react withalkenylzirconocenes, and offer the enimines. This reaction can proceed under mild conditionswith a wide range of functional groups. These products can be characterized by NMR spectra,and the structure of the product was characterized by a two-dimensional NMR spectra.Part III, The reported methods to synthesis enamides almost used the amides as the nucleophiles. we found that the azide as the nitrogen source has been rarely repoted. So in thisdissertation, we used the azides to react with alkenylzirconocenes, and we can also producethe enamides, this reaction can also proceed under mild conditions with a wide range offunctional groups, and the structure of the product cab be characterized by single-crystalX-ray and IR spectra.