Study On The Metallic Samarium Promoted C-C Coupling Reactions Catalyzed By Inorganic Salts

Carbon-carbon coupling is one of the important methods of organic synthesis.There are many methods of carbon-carbon coupling,among which the interaction between various metals can be used to construct new C-C bonds,which is of great significance in the development of new compounds and improvement of traditional synthesis methods.This paper describes a new method to promote carbon-carbon bond coupling by the interaction between Sm and Cu I(Mn Cl2,Li Cl,Al Cl3 and other inorganic salts)under the condition of anhydrous and anaerobic conditions.This method expands the application of metal samarium and opens up some new reactions in which multiple metals cooperate to promote organic synthesis.Firstly,under the catalysis of Cu I,the metal samarium promoted benzaldehyde self-coupling and in situ condensation reaction with ester was investigated.A series of experiments were designed to explore the reaction conditions in detail,and finally the optimal reaction conditions were obtained,and a model reaction was established,and the applicability range of ester and benzaldehyde was further studied.By analyzing the influence of different aromatic aldehydes and esters on the reaction results,the reaction rules were summarized from the aspects of electronic effect and steric hindrance.In the study process,a series of experiments were designed to study the cross-coupling reaction mechanism of benzaldehyde,and the reaction mechanism was preliminarily explored,and the possible reaction course was proposed.Secondly,the research on the coupling reaction between halogenated benzene and DMF promoted by metal samarium catalyzed by Cu I is mainly about the optimization of reaction conditions and the exploration of the reaction between dihalogenated compounds and DMF.Finally,it was found and explored that Sm and Mn Cl2 synergically promoted carbon-carbon coupling reaction,which was also an important discovery in the combination of inorganic salts and metal samarium.Mn Cl2 was successfully combined with Sm and carbon-carbon coupling was realized.First,catalyzed by Mn Cl2 and promoted by Sm,benzyl bromide successfully reacted with paraformaldehyde to form dibenzyl ether.Sm and I2 could also make benzyl bromide react with paraformaldehyde,but the reaction was far from good.Then,the reaction conditions of benzyl bromide and paraformaldehyde were optimized,and according to the experimental results,paraformaldehyde participated in this reaction.Second,catalyzed by Mn Cl2 and promoted by Sm,benzyl bromide was used to react with DMF and obtain an unexpected phenacetaldehyde.Therefore,the reaction between halide and DMF promoted by Sm under the catalysis of Mn Cl2 was explored.In this system,the reactions of a series of halogenated hydrocarbons(benzene halide,Halogenated fatty hydrocarbons,benzyl halogenated hydrocarbons,etc.)with DMF were investigated in detail.The results show that bromine can obtain corresponding products with good yield;But the effect of chlorobenzene and iodobenzene reaction was poor.Therefore,the reaction has high selectivity.Thirdly,other reactions of Sm-promoted benzyl bromide with phenylacetaldehyde,phenylpropyl aldehyde,and benzophenone catalyzed by Mn Cl2 were also attempted and explored.A total of 61 products were obtained in this experiment.Data and graphs of 1H NMR,13 C NMR,HRMS and X single crystal diffraction of the product are shown in appendix 1 and 2.