Synthesis, Characterization, And Catalytic Application Of Macmillan Catalysis Functionalized Phenolic Resin Material

Imidazolidinone, the so-called MacMillan catalyst, which was developed by MacMillan et al. in2000, is now one of the most privileged and versatile organocatalysts and has been utilized in a variety of highly enantioseletive reactions. One of the major bottlenecks of MacMillan catalyst, however, is the low efficiency of catalyst and the difficulty in recycling of the catalyst, which may restrict its applications in large scales. An attractive solution to such drawbacks, may be the heterogenization of MacMillan catalyst, which was commonly achieved by post-grafted methods. However, these post-grafted approaches still exist several shortcomings, such as less and uneven distribution of catalytic site, unstableness and mass transport issues, accordingly, numerously suffering from a significant drop of activity compared to their homogeneous counterparts. Therefore, the development of new approaches for the heterogenization of MacMillan catalyst, accordingly, has the important scientific significance and practical value.Accordingly, the research work described in this thesis was closely around the above-mentioned issues, and was mainly focused on:1) the "bottom-up" construction of MacMillan catalyst functionalized phenolic rein and its heterogeneous catalysis applications;2) construction of MacMillan catalyst functionalized ordered mesoporous phenolic resin via a solvent evaporation induced self-assembly method, by the assistance of a template.In Chapter Ⅰ, we reviewed the applications of MacMillan catalyst as homogeneous and heterogeneous catalysts, the "bottom-up" construction of heterogeneous catalysts, and the applications of porous materials in heterogeneous catalysis.In Chapter Ⅱ, we have reported the synthesis, characterization and heterogeneous catalysis application of MacMillan catalyst functionalized phenolic reins. Firstly, we synthesized two MacMillan catalyst derivatives4and6containing a phenol group from very cheap valine. Then linear MacMillan catalyst functionalized phenolic reins was synthesized via the condensation of4or6with formaldehyde in the presence of NaOH; meanwhile, we also obtained reticular MacMillan catalyst functionalized phenolic reins through the addition of phenol during the synthetic process. We then examined the catalytic activity of MacMillan catalyst functionalized phenolic reins using the asymmetric Diels-Alder reaction of (E)-cinnamaldehyde and cyclopentadiene as a model reaction. The results demonstrated that our catalysts showed comparable enantioselectivities and slightly lower activities with their monomeric analogues.In Chapter Ⅲ, we have reported the synthesis of MacMillan catalyst functionalized ordered mesoporous phenolic rein. Using the A-step phenolic rein starting from4, phenol and formaldehyde as a precursor, MacMillan catalyst functionalized ordered mesoporous phenolic rein was synthesized via a solvent evaporation induced self-assembly method, by the assistance of a template, which was preliminarily characterized by solid state NMR and Powder XRD.