Synthesis Of BINAP-Ru-BINAM Complex And Studying Its Catalytic Properties

Chirality is one of the basic attribute living organisms which dominates the various life activities, chiral material needs tremendous, the most effective way to obtain chiral compounds is asymmetric synthesis.In the past forty years, asymmetric catalytic hydrogenation got the rapid development and achieved many remarkable achievements. Scientists synthesized a series of excellent performance of catalysts.We designed and synthesized a form of metal complex of double triarylphosphine ligand-Ru-diamine ligand, applied them to asymmetric catalysis hydrogenation reaction of acetophenone, and investigated the catalytic properties of the metal complex.In the process of research, mainly works as following:1.On the basis of concluding previous work, improving the synthesis of rac-binol. In the function of ultrasonic, completing coupling reaction of 2- naphthol, simplifing the experiment steps, and achieving yield of 80%.Comprehensivily using of two kinds of split agent 2-pyrrolidone-5- carboxyanilide and (8S,9R)-(-)-N-benzalhydantoin to resolute of rac-BINOL.The split effect of 2-pyrrolidone-5-carboxyanilide:the yield of R-and S- is respective 18.1% and 37.6%, split agent recovery70%.The split effect of (8S,9R)-(-)-N- benzalhydantoin: the yield of R-and S-is respectively 94% and 96%, split agent recovery 95%. Choosing (8S,9R)-(-)-N-benzalhydantoin to resolute of rac-BINOL according to comparison of optical resolution process and effect.2.The synthesis of BINAP is using 1,1'-binaphthol as starting material according to esterification and substituent to get. And the yield of R/S-BINAP respectively are 54.6% and 60%.3.The synthesis of BINAM bases onβ-naphthol as raw materials, in the condition of high temperature and pressure, reacting with ammonium hydrogen sulfite to getβ-naphthylamine, then coupling in the interaction of copper chloride and ethanolamine with yield of 80%.4.Use of d-(+)-camphor sulfonic acid split the rac-BINAM, chiral BINAM is got as diamine ligand amine. The yield of two isomer(S-;R-) are 95% and 70% respectively. Both of enantiomers can be obtained with>99%. The yield of S-BINAM is 6% more than literature.5.The complex of BINAP-Ru-BINAM is got and applied to the asymmetric hydrogenation of acetophenone. The catalytic properties of the complex is examined. Conversion rate of acetophenone is 99.6%, enantiomers can be obtained only with 7.1 %.