Coupling Reaction And Transformation Of Organobismuth Chloride With Alkyl Halogenated Hydrocarbons Catalyzed By Iron

The transition metal-catalyzed reductive coupling reaction refers to the coupling reaction between two electrophiles with the participation of a transition metal catalyst and a reducing agent.Transition metal-catalyzed reductive coupling reactions have been widely used in fine chemicals,pharmaceuticals,agrochemicals,as well as multifunctional organic molecules and complex natural products due to their advantages of step economy,chemoselectivity,and wide applicability of substrate functional groups.synthesis.Metal-organic reagents have been widely studied as the most commonly used coupling reagents in the construction of carbon-carbon bonds and carbon-hetero bonds.Among the currently known organometallic reagents,organolithium reagents,Grignard reagents,organozinc reagents,etc.Most of the metal reagents are sensitive to water and oxygen,and have poor tolerance of functional groups,which limit their further applications.Nitrogen-bismuth octyl ring organobismuth halides have unique advantages of water resistance and oxidation resistance.Therefore,combining the advantages of reductive coupling reaction with the advantages of nitrogen-bismuth octyl ring organobismuth halides,a class of water-resistant and antioxidant-type organobismuth alkyl groups was synthesized.It is possible to couple reagents and make them widely used alkylating reagents.The second chapter of this thesis introduces an iron-catalyzed method for the synthesis of alkylbismuth compounds through the reductive coupling of alkylhalohydrocarbons with nitrogen-bismuth octacyclic organobismuth halides.In this method,various alkyl halohydrocarbons as well as organobismuth halides containing different substituents were experimentally explored.In this method,the reaction catalysts,additives,reducing agents,reaction solvents,reaction temperatures and reaction times were screened in detail,the optimal reaction conditions were established,and the tolerance of substrate functional groups,ester groups,cyano groups,ethers,Acetal,carbon-carbon double bond and carbon-carbon triple bond can be well tolerated,and the method has good cross-coupling selectivity.Further control experiments show that there may be multiple reaction paths for this reaction,and the target product can still be obtained in moderate yields without catalyst,indicating that organic manganese reagents may be generated during the reaction process,and the reaction yield is greatly improved in the presence of catalysts,indicating that The iron-catalyzed catalytic cycle is the main reaction pathway.The third chapter of this thesis introduces a palladium-catalyzed cross-coupling reaction of the above water-resistant and oxygen-resistant alkylbismuth compounds with aryl halides.This method realizes the highly selective cross-coupling of C(sp3)and C(sp2).Further studies show that this method is more favorable for the conversion of aryl halides containing electron withdrawing groups.The method has the characteristics of mild reaction conditions,high product selectivity,and a wide range of substrate adaptation.It provides a reference for the activation of sp3 carbon-metal bonds.