preparation of metal-oxo complex bearing tridentate ligand: development of asymmetric oxidation reaction assisted by additional ligand

在此基础上，设计了一种由附加配体控制的不对称氧化催化剂。铁卟啉类化合物是一种重要的氧化催化剂，但由于其平面结构，使其在不对称氧化反应中的应用变得困难。经过多次尝试，我发现铁-cazbox配合物催化烯烃的不对称环氧化反应。通过ESR和UV的机理分析表明，cazbox配体在氧化反应中表现出与卟啉类似的反应活性。此外，对配体取代基效应的研究表明，产物的对映选择性依赖于cazbox配体与相应底物之间的电子相互作用。通过这些研究，我开发了具有类卟啉反应活性的手性配体CAZBOX。

On this study, an asymmetric oxidation catalyst controlled by an additional ligand was designed. Although iron-porphyrins are well-known catalysts for oxidations, application of them to asymmetric oxidation are difficult due to their planar structure.I focused on CAZBOX ligand, which has porphyrin-like structure such as planarity and amide-ligands. After numerous attempts, I found that the iron-cazbox complexes catalyze asymmetric epoxidations of alkenes. Mechanistic analyses by ESR and UV present the cazbox ligands show similar reactivity to porphyrins on the oxidation reactions. Furthermore, studies on substituent effect of the ligand disclose that enantioselection of the product depend on electronic interaction between the cazbox ligand and the corresponding substrate. Through these studies, I have developed the chiral ligand CAZBOX bearing porphyrin-like reactivities.