Study On Copper-catalyzed Samarium-mediated Carbon-carbon Bond Reductive Coupling Reaction

The construction of the diaryl skeleton and the formation of carbon-carbon bonds are still one of the hottest topics in current organic synthesis field.The development and use of samarium reagents and copper reagents is important for the methodology of forming carbon-carbon bonds.In this paper,the application of samarium-copper catalytic reduction system in this aspect is mainly studied.The purpose is to further expand the application range of samarium reagent in organic synthesis in the presence of copper.The content of the thesis consists of four chapters.The first chapter is a literature review,which mainly introduces the application of bismuth reagent,copper reagent and N,N-dimethylformamide in organic reaction.In particular,the use of divalent samarium in coupling cyclization and functional group reduction,and the use of copper reagents in the formation of carbon-carbon bonds and carbon-hetero bonds is introduced in detail,and a brief introduction of N,N-dimethylformamide as a raw material is demonstrated.In the second chapter,the coupling reaction of samarium-copper iodide catalyzed three components of halogenated hydrocarbon,DMF and ester was studied.It was found that in a DMF solvent the use of a halogenated hydrocarbon provided a diaryl carbonate product in good yield.The reaction with an electron-withdrawing halogenated hydrocarbon was less effective than that of a halogenated hydrocarbon with an electron-donating group.The reaction of diethyl carbonate with dimethyl carbonate was even less effective,and the reaction cannot be carried out in diphenyl carbonate and ethylene carbonate.The third chapter is the study of the coupling reaction of aromatic aldehyde catalyzed by samarium-copper iodide.On the basis of the previous chapter,the adaptability of the aromatic aldehyde to the reaction was attempted,and the diaryl carbonate product was successfully obtained.Different substituted aromatic aldehydes have good adaptability to the reaction,and experiments on cross-coupling reactions between different aromatic aldehydes have been carried out.Unfortunately,the effect was not ideal,and the product was mainly homologous coupling,not cross-coupling.The fourth chapter studies the self-coupling reaction of halogenated hydrocarbons catalyzed by samarium-copper chloride.It was found that the use of benzyl halides could obtain a bibenzyl product in high yield,and benzyl halides with electron donating groups have more reactivity,higher yield and less reaction time than benzyl halides with electron withdrawing groups.Under the same reaction conditions,the use of aryl halide could only bring a moderate yield.At the same time,experiments have shown that potassium iodide is essential to the reaction.In the paper,the reaction mechanism was verified and studied,and the possible reaction mechanism was discussed.The obtained compounds were tested by ¹H NMR,¹³C NMR and Single Crystal X-ray Diffraction.The characterization data and spectra of the products are shown in the Appendix...