Synthesis Of Chiral Guanidine Ion Liquid, Nature Study, And Arylation Of Active Methylene Compounds Reaction

This thesis was focused on two sections. In the first section, chiral guanidinium-based ionic liquids were synthesized and characterized. In the second section, we described CuI/L-proline-promoted cross-coupling reaction of aryl iodides with activated methylene c-ompounds.With the development of ionic liquids, a great deal of recent attention has focused on the functionalized ionic liquids. As one of the functionalized ionic liquids, chiral ionic liquids have great potential in asymmetric organic reactions. On the other hand, chiral guanidine catalysts are attractive targets in organocatalysis. We designed and synthesized chiral guanidinium-based ionic liquids. First, Chiral guanidinium chloride salt was synthesized from 1, 3-dimethyl-2-imidazolidinone, (S)-Phenyl-ethyl-amine. Then 14 ionic liquids with different anions are obtained by metathesis reactions of Chiral guanidinium chloride with MX and characterized. In addition, we investigated the reaction of benzaldehyde with nitromethane catalyzed by chiral guanidinium-based ionic liquids.In the second section, the cross-coupling reaction of aryl iodides with activated methylene compounds under the catalysis of CuI/L-Proline was investigated. After screening solvents, ligands and reaction temperature, we found the optimized reaction conditions for this transformation conditions were 10mol% CuI, 20mol% L-Proline, 1eq. 1-iodobenzene, 3eq. pentane-2, 4-dione, 4eq. K₂CO₃, DMSO as solvent, and 90°C as reaction temperature. Both electron-rich and electron-deficient aryl iodides were compatible with these conditions, giving the corresponding 3-aryl-2, 4-pentanediones in good yields. Under the same conditions, the cross-coupling reaction of substituted aryl iodides with ethyl-2-cyanoacetate catalyzed by CuI/L-proline was also provided α-aryl cyanoacetates in good yield.