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有机合成中的锆基催化剂

Zirconium-Based Catalysts in Organic Synthesis.

作者信息

Peng Lifen, Zhao Yanting, Yang Tianbao, Tong Zhou, Tang Zilong, Orita Akihiro, Qiu Renhua

机构信息

Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, 411201, Hunan, China.

State Key Laboratory of Chemo/Biosensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China.

出版信息

Top Curr Chem (Cham). 2022 Aug 11;380(5):41. doi: 10.1007/s41061-022-00396-4.

Abstract

Zirconium is a silvery-white malleable and ductile metal at room temperature with a crustal abundance of 162 ppm. Its compounds, showing Lewis acidic behavior and high catalytic performance, have been recognized as a relatively cheap, low-toxicity, stable, green, and efficient catalysts for various important organic transformations. Commercially available inorganic zirconium chloride was widely applied as a catalyst to accelerate amination, Michael addition, and oxidation reactions. Well-designed zirconocene perfluorosulfonates can be applied in allylation, acylation, esterification, etc. N-Chelating oganozirconium complexes accelerate polymerization, hydroaminoalkylation, and CO fixation efficiently. In this review, the applications of both commercially available and synthesized zirconium catalysts in organic reactions in the last 5 years are highlighted. Firstly, the properties and application of zirconium and its compounds are simply introduced. After presenting the superiority of zirconium compounds, their applications as catalysts to accelerate organic transformations are classified and presented in detail. On the basis of different kinds of zirconium catalysts, organic reactions accelerated by inorganic zirconium catalysts, zirconium catalysts bearing Cp, and organozirconium catalysts without Cp are summarized, and the plausible reaction mechanisms are presented if available.

摘要

锆在室温下是一种银白色的可锻且有延展性的金属,在地壳中的丰度为162 ppm。其化合物表现出路易斯酸性行为和高催化性能,已被认为是用于各种重要有机转化的相对廉价、低毒、稳定、绿色且高效的催化剂。市售的无机氯化锆被广泛用作催化剂以加速胺化、迈克尔加成和氧化反应。精心设计的全氟磺酸二茂锆可用于烯丙基化、酰化、酯化等反应。N-螯合有机锆配合物能有效加速聚合、氢胺烷基化和一氧化碳固定反应。在本综述中,重点介绍了市售和合成的锆催化剂在过去5年有机反应中的应用。首先,简要介绍了锆及其化合物的性质和应用。在阐述了锆化合物的优势之后,将其作为催化剂加速有机转化的应用进行了分类并详细介绍。基于不同类型的锆催化剂,总结了无机锆催化剂、含茂基锆催化剂和不含茂基有机锆催化剂加速的有机反应,并在可能的情况下给出了合理的反应机理。

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