Synthesis And Application Of Catalytic Epoxidation Of Novel Chiral Ruthenium Porphyrin

This thesis describes maily about the synthesis and application of asymmetrical chiral porphyrin. A chiral group and different steric hindrance groups were introduced into the meso-positions of the porphyrin cyclo, so a series of hybrid porphyrin were prepared. Then these porphyrins were converted into Ru porphyrin catalysts. The catalysts were applied for unsymmetrical epoxidation of unfunctional small olefins. The primary research indicated that the porphyrin catalysts have good reaction activity and enantio selectivity. This result suggested that we may make great progress in the unsymmetrical epoxidation of unfunctional small olefins.The work of this thesis contains the following two parts:The fist, a new high hindrance chiral porphyrin was designed according to some literature. Two paths were selected:"step by step" and "one pot". Based on experimental study, we found that the "step by step" path was difficult to handle and needs further investigation. Via the "one pot" path, three hybrid chiral porphyrin were obtained after repeatedly flash chromatography. Furthermore, a C2 symmetrical chiral porphyrin was prepared in high yield, which is a crucial supplement of the porphyrin of the "one pot" route. By far,2,4,6-trimethyl phenyl aldehyde and 2,4,6-triphenyl phenyl aldehyde react with chiral aldehyde, respectively, affording the relative porphyrins. The chiral aldehyde was accumulated which is the basic material for the further research.The second, the chiral porphyrins were converted into Ru-porphyrin catalysts, and used in the unsymmetrical epoxidation of unfunctional small olefins. The ee values are detemined by 1H NMR with Eu(hfc)3 as shift reagent. The results showed that the novel porphyrins have better catalysis activity and enantio selectivity for unfunctional small olefins. The ee value was up to 79% under a raw reaction condition, further study is under way.