超分子化学与催化的不断渗透融合催生了超分子催化这一挑战性的前沿研究热点。作为超分子化学的主要研究对象，大环化合物因具有可以和不同客体分子通过非共价相互作用可逆结合的识别位点，模拟酶催化中对底物分子的预组织过程，在超分子催化发展之初就备受关注，并在近二十年来取得了可喜的发展。本综述主要介绍了近十年来发展的基于冠醚、环糊精和杯芳烃等大环主体分子的代表性手性超分子催化剂，以及它们在不对称催化反应中的应用，重点阐述了主-客体等弱相互作用对催化剂活性和对映选择性的超分子调控作用，同时对这一研究领域目前存在的局限性和不足进行了总结，并展望了不对称超分子催化的发展前景。
In recent years, supramolecular catalysis has become one of the most challenging research frontiers and hot spots in organic synthesis based on the continuous combination and fusion of supramolecular chemistry and catalysis, and has achieved gratifying development. As the main objectives in supramolecular chemistry, macrocyclic host molecules have gained much attention in supramolecular catalysis due to their reversible recognition and self-assembly with different guest molecules and thus can realize pre-organization of reactants within the catalytic cavities. In the last 20 years, progress has been achieved in supramolecular catalysis based on macrocyclic host molecules. This review will focus on the recent progress in asymmetric supramolecular catalysis based on the representative macrocyclic host molecules, such as crown ethers, cyclodextrins, calixarenes, and their counterparts. The design and synthesis of chiral catalysts, the use of these catalysts in enantioselective reactions, especially, the supramolecular modulation of catalytic activity and selectivity via host-guest association will be introduced. Meanwhile, the limitation and drawbacks of current study and the perspectives for its future development will also be discussed.
Contents
1 Introduction
2 Asymmetric catalysis based on crown ethers and their counterparts
2.1 Chiral crown ether-based metal catalysts
2.2 Chiral metallacrown ether catalysts
2.3 Chiral pseudorotaxane and rotaxane catalysts
2.4 Podands in asymmetric catalysis
3 Asymmetric catalysis based on cyclodextrins
3.1 Cyclodextrin as macroreactor
3.2 Cyclodextrin-based metal catalysts
3.3 Cyclodextrin organocatalysts
4 Asymmetric catalysis based on chiral calixarenes
4.1 Chiral calixarene-based metal catalysts
4.2 Chiral calixarene-based organocatalysts
4.3 Inherently chiral calixarene catalysts
5 Conclusion and outlook
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