CuI-Catalyzed C-C Bond Coupling Reactions Mediated By Samarium Reagents

The coupling reactions can be seen as a cornerstone of organic synthesis,the C-C bonds formation has occupied the most important position in coupling reactions.Samarium belongs to rare metal,and the Samarium reagent has superior reductive coupling ability,which plays an important role in the formation of C-C bonds,carbon-heterobonds,and heteroheterobonds.Meanwhile,Copper reagent shows unique catalytic coupling properties,and it have a wide range of applications in organic synthesis.Samarium metal was used as the reaction reagent directly,it combined with the catalytic coupling ability of cuprous,Develop new organic reaction methods,realize carbon-carbon bond coupling efficiently,and research the mechanism of the combined of samarium metal and cuprous.It has a great significance to the application of samarium chemistry and copper chemistry,the completely development and utilization of rare earth resources.This work focuses on study of the C-C bonds coupling reaction after the intervention of samarium reagent under the catalysis of Cu I,aiming to develop and expand the new application in organic synthesis as well as study the mechanism of combination with transition metal.Mainly contents as the following.The research of samarium and copper reagents about organic synthesis in recent years is introduced in first part literature reviews.It mainly introduces the application of SmI₂,Sm,and copper in the synthesis of C-C bonds and carbon-heterobonds.The study of reductive coupling reaction of amide and nitrile with diaryl ketone in the presence of Sm/I₂/Cu I is introduced in second chapter.Nitriles（acetonitrile,butyronitrile,isobutyronitrile,etc.）and amides（N,N-dialkyl substituted amides,pyrrolidone,etc.）successfully couple with diaryl ketones in the optimal conditons.The new deoxycoupling product was discovered after increasing the temperature as well as proposed the possible mechanism.The reaction catalyzed by Cu I and promoted by I₂,which introduce samarium metal into the reaction under conditions without any ligands.The merits of reaction include mild conditions,simple operate,and the solvent itself used as a substrate,good efficiency.The research of addition reaction of organic halogens and carbonyl compounds in the presence of Sm/Cu I was developed in third chapter,as well as discovered the reaction of Sm/Cu I-mediated Barbier-type high-efficiency addition of halogenated hydrocarbons and carbonyls.By optimizing the reaction conditions,it was found that the reaction only requires the combined use of Cu I and Sm and no longer requires the participation of other activators to smoothly carry out the addition reaction of halogenated hydrocarbons and carbonyl compounds.The range of substrates is very wide,such as aldehydes,ketones,acid chlorides,acid anhydrides,esters,amides,etc.Combining the results to design a verification experiment,the reaction of the organic samarium intermediate is proposed.The conditions are mild and efficient,it can be realized by one-pot method without ligands.A series of compounds synthesized in the research have completed the spectral characterization,including ¹H NMR,¹³C NMR,IR and single crystal X-ray diffraction,etc.The relevant characterization data and spectra are shown in the appendix.Numbers of products obtained in the research it has completed the spectral characterization,including ¹H NMR,¹³C NMR,IR,etc.The relevant characterization data and spectra are shown in the appendix.