手性卟啉铁与钴的配合物在不对称催化合成中的应用

Application of Chiral Porphyrin of Iron and Cobalt Complexes in Asymmetric Catalysis

摘要: 本综述类论文阐述了手性卟啉铁、钴配合物在不对称催化领域的研究进展与应用前景。重点围绕手性侧链修饰策略，深入探讨了铁、钴卟啉催化剂在环氧化、环丙烷化、C-H键胺化等重要有机转化中的催化性能与机理特征。从Groves开创的“手性口袋”到Collman发展的“栅栏”卟啉，再到现代C2对称、D4对称等精密结构设计，手性环境的构建日趋精细。催化反应从最初的不对称环氧化，逐步发展到环丙烷化、C-H键胺化、氮杂环化等多种类型，底物适用范围不断扩大，对映选择性不断提升。本论文内容展现了手性金属铁、钴卟啉从仿生模拟到功能创新的发展历程，为设计新一代高效、高选择性仿生催化剂提供了重要理论基础与实践指导。随着对金属中心特性与手性微环境相互作用机制的深入理解，手性金属卟啉催化剂必将在不对称合成、药物制备和绿色化学等领域发挥更加重要的作用。

Abstract: This paper reviews the research progress and application prospects of chiral porphyrin-iron and-cobalt complexes in the field of asymmetric catalysis. Focusing on chiral side-chain modification strategies, the catalytic performance and mechanistic features of iron and cobalt porphyrin catalysts in key organic transformations such as epoxidation, cyclopropanation, and C-H amination are explored in depth. From the “chiral pocket” pioneered by Groves to the “picket fence” porphyrin developed by Collman, and further to modern sophisticated structural designs such as C2-symmetric and D4-symmetric architectures, the construction of chiral microenvironments has become increasingly refined. Catalytic reactions have evolved from the initial asymmetric epoxidation to encompass diverse types such as cyclopropanation, C–H amination, and aziridination, with continuously expanding substrate scope and steadily improving enantioselectivity. The content presented in this paper illustrates the developmental trajectory of chiral iron and cobalt metalloporphyrins from biomimetic simulation to functional innovation, providing a significant theoretical foundation and practical guidance for the design of a new generation of highly efficient and selective biomimetic catalysts. With the deepening understanding of the interaction mechanisms between metal center properties and chiral microenvironments, chiral metalloporphyrin catalysts are poised to play an increasingly vital role in areas such as asymmetric synthesis, pharmaceutical manufacturing, and green chemistry.