Study On The Double Addition Reaction Of ?,?-unsaturated Compound By Sm/CuI/KI

This thesis is divided into four chapters to discuss, first part summarizes the synthetic applications of samarium reagents, copper reagents and ester-exchange reaction in recent years. The second chapter is description of the research of samarium/ copper salt/potassium iodide/4A molecular sieve promotion of aromatic aldehyde and acrylate derivatives double addition coupling reaction. The third chapter contains the research of aromatic aldehydes and maleic acid ester double addition reaction in samarium/copper salt/potassium iodide system and samarium/copper salt/potassium iodide/4A molecular sieve system.The first chapter mainly includes the following contents:(1) samarium reagents in organic synthesis application and development of prospects;(2) copper reagents in organic synthesis development;(3) ester exchange reactions of a variety systems and switching methods.The second chapter detailed describes aromatic aldehyde and acrylate ester derivatives of coupling cyclization reactions in the Sm/Cu I/KI/4A molecular sieve system, mainly includes the following contents:(1) optimization of reaction conditions for aromatic aldehydes and acrylate derivatives, such as optimization of catalytic system, optimization of substrate ratio and catalyst ratio, optimization of reaction temperature, solvent and reaction time, optimization of the reaction of auxiliary reagents and ligands, the reaction of different aromatic aldehydes and acrylate derivatives;(2) the reaction of benzaldehyde and methyl acrylateother promoted by the other copper reagent;(3) the reaction of benzaldehyde and methyl acrylateother promoted by Ag NO3/Sm/Cu I;(4)the innovation and mechanism of reaction.The third chapter mainly introduces the coupling reaction of aromatic aldehydes and maleic acid ester, mainly includes the following contents:(1) reaction research of aromatic aldehydes and maleic acid ester, such as effects of catalytic system, selection of catalyst and the ratio of substrates, the optimization of reaction temperature, reaction solvent, reaction time, reaction of different aromatic aldehydes and maleic acid ester, effects of the reaction by molecular sieve and methyl benzene sulfonic acid;(2) the innovation and mechanism of reaction.The fourth chapter introduces the experimental procedure of aromatic aldehyde and acrylate ester derivatives under different systems and the experimental procedure of aromatic aldehyde and maleic acid ester under different systems.In this paper, we introduces the coupling reaction of aromatic aldehydes and acrylate by Sm/Cu I/KI/4A molecular sieve system, synthesize 2-(hydroxymethyl)-phenyl-4-phenyl-?-butyrolactone compounds; introduces the coupling reaction of aromatic aldehydes and maleic acid ester by Sm/Cu I/KI system, synthesized 2,3-bis(hydroxymethyl)-phenyl succinic acid diethyl ester compounds and 2-(hydroxymethyl) phenyl-3-carboxylicacidester-4-phenyl-?-butyrolactone compounds, introduces the coupling reaction of aromatic aldehydes and maleic acid ester by Sm/Cu I/KI/4A molecular sieve system, synthesize 3,6-diphenyl-tetrahydro-furo[3,4-c]furan-1,4-dione compounds. All reactions are synthesized by one pot method, making the operation simple. These reactions are in favor of protecting groups under mild condition and break employ limitation of the traditional samarium reagents by nitrogen protection. At the same time, these reactions are double addition of C=C double bond, which is of great significance in organic synthesis.