The Study On The Transition Metalscatalyzed Coupling Reactionsmediated By Samarium Metal

In this paper,the catalytic and reduction systemsabouttransition metals and samarium metal which applied in the coupling reactionswere studied.The aim of this study is to expand the application of samarium metal in organic synthesis.The first chapter is the review of literatures,we mainly introduced the research progress of samarium reagents and transition metalscatalysis in organic reactions.In this part,samarium diiodide,samarium metal and samarium triiodide wereintroducedin detail.The application of transition metals in the field of organic synthesis is very wide,and the formation of carbon and carbon bonds and the cleavage and formation of carbon and heteroatomwere briefly introduced in this part.In the second chapter,the homocoupling reaction of organohalides catalyzed by NiCl2 and mediated by samarium metal was studied.It was found that the catalytic and reduction system of NiCl2/Sm/HMPA could catalyze the homocoupling reaction of organohalidesafter a series of experiments,and then we optimized the reaction conditions.Under the optimum reaction condition,the tolerable substrate ranges include benzyl halides,aryl halides,heterocyclic halides,alkenyl halides,alkyl halides,?-halo-acetophenones and phenyl organosulfonates,covering two types about Csp3-Csp3 and Csp2-Csp2.Finally,the possible mechanism of the reaction was deduced by combining the stereoselectivity of the reaction and some exploratory experiments.In this reaction,NiCl2 was used as a catalyst,and samarium metal was introduced into this reaction in the absence of ligand,HMPA was used as an addition agent.Mild condition,simpleoperation both are the characteristic of this reaction,andthe mostimportant is excellent chemoselectivity and stereoselectivity.The organic reaction catalyzed by copper iodide and mediated by samarium metal was studied in the third chapter,including the Barbier reaction and the homocoupling reaction of halohydrocarbon.Firstly,we have studied the Barbier reaction of halohydrocarbonwith carbonyl compounds mediated by CuI/Sm,and we found that the addition reaction of halohydrocarbon with carbonicesterscan go well mediated by the combination of copper iodide and samarium metal without other additives.The carbonyl compounds were extended further,and it was found that aldehydes,ketones,acyl chlorides,anhydrides,esters,amides and so on can react with halohydrocarbon to produce different kinds of compounds respectively.Then,the reaction of aryl halides with DMF mediated by CuI/Sm was also studied in detail,and got a series of aldehydes.It was also found that the homocoupling reaction of halohydrocarbon mediated by CuI/Sm couldrealize successfully.The optimum reaction condition was explored,and the reaction substrates were expanded initially.Finally,the possiblemechanisms about organic samarium intermediates of these reactions were discussed.At present,further research is still ongoing.Aseries of compounds including aldehydes,ketones,alcohols,andso on have processed a complete spectral characterization,including 1H NMR,13 C NMR,IR,and related characterization data were showed in the appendix.