Synthesis And Application Of Catalytic C-H Hydroxylation And Amination Of High Steric Hindrance Chiral Ruththenium Porphyrin

Chiral metalloporphyrins have unique structures, and they are superduper chiral catalysts for asymmetric catalytic oxidation of hydrocarbons under mild conditions. Although there are some difficulties in the synthesis of chiral porphyrins, chemists are still interested in the design and synthesis of the novel chiral porphyrin structures. According to the reported results about the chiral metallporphyrins catalyzed reactions, the meso-chiral substituted groups and the meso-space steric substituted groups are related to their enantioselectivity and activity. Therefore, design and synthesis of high enantioselective and high active chiral metalloporphyrins are still a challenge to explore the superduper chiral porphyrin catalyst.The functionalization of saturated C-H bond is currently an important research direction in chemistry research area. There is an urgent and challenging problem:how to achieve high enantioselectivity of C-H asymmetric functionalization. The bionic metalloporphyrin catalysts have the advantages of high stability and high TON. Through oxygen atom, nitrogen atom and carbene transfer process, the saturated C-H bond hydroxylation, amination and alkylation can be realized. And the reactions exhibit high catalytic activity and potential high enantioselectivity.This thesis focused on the preliminary exploration on the synthesis of a series of chiral porphyrins and its application on asymmetric catalytic reactions, including the asymmetric hydroxylation and the asymmetric amination of benzyl C-H. The content includes as followings:The first part, according to the literatures, we have introduced different chiral fragments and different space steric groups in the porphyrin ring meso positions to design and synthesize a series of bulky hybrid porphyrins. In order to get the target porphyrins, we adopted a "step by step" method and a "one pot" route in synthesis. In this way,we can obtain different bulky chiral hybrid porphyrins.On the other hand, we transformed the chiral hybrid porphyrins into Ru-porphyrins, and used them to catalyze asymmetric hydroxylation and amination reactions of benzyl C-H. Then we measures the products’ ee values by HPLC. Firstly, in order to get standard samples, we used achiral porphyrins to catalyze these reactions. Then we detected the enantioselectivity of the products catalyzed by chiral Ru-porphyrins.