Chiral Schiff Base-Copper(Ⅱ)Complexes Catalyzed Asymmetric Reactions

This thesis was mainly developed two aspects of Schiff base-copper(Ⅱ) catalyzed direct enantioselective vinylogous Michael addition of a, P-unsaturated y-butyrolactam to nitroolefins and Schiff base-copper(Ⅱ) catalyzed enantioselective Friedel-Crafts alkylation of pyrrole with isatins. The first part discusses the asymmetric synthesis method of chiral α,β-unsaturated y-butyrolactams and the second part discusses the asymmetric synthesis method of chiral3-substituted3-hydroxy-2-oxindoles.y-Butyrolactam is an important structural unit exists in a vast array of natural products and drug candidates. Recently, several reports have been published about the synthetic methods of this structure, while the reports of direct synthetic method about this structure are seldem. With the development of chemistry and the society, people pay more and more attention to environmental protection and economy, green chemistry has become a main tendency. Atom economy as one of the most important contents has attracted the attention of many organic chemists. Because the traditional synthetic methods usually use substracts with protection groups or the products have to transferred with more steps to obtain the final y-butyrolactams, it dosen’t fit the concept the atom economic. The direct synthesis of y-butyrolactams is the most atom economic method. Because the direct synthesis methods about this structure is seldom, it necessary to develop more different catalysts to synthesis this structure. The first part of the thesis discusses the direct asymmetric synthetic method of y-butyrolactams with our lab developed Schiff base-copper(Ⅱ) catalysts.Chiral3-substituted3-hydroxy-2-oxindoles is another important structural unit. Recently reports about catalysts of the synthesis of this structure contain metal catalysts and organic catalysts, while there is only one report about the Friedel-Crafts alkylation of pyrrole with isatins, so it has great significance to develop the methods to synthesis this structure. The second part of the thesis discuss the copper-catalyzed enantioselective Friedel-Crafts alkylation of pyrrole with isatins. The main problem of this research is to promote the enantioselective value of the products, here we successfully find a reaction additive-HFIP to enhance the selectivity of products. More importantly, we develop a slow-releasing strategy to solve incompatibility of N-unprotected isatins. Finally, based on the absolute configuration of the products and some mechanism study experiments, we proposed a rational model to explain the reason of the absolute configuration.The chapter one of the thesis was about the simple reviews of asymmetric vinylogous reaction, the asymmetric Michael addition and the asymmetric Friedel-Crafts reaction. The chapter four is the experiment section, mainly about the manipulations of the experiments and the property data of some compounds.