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双功能手性金属络合物催化的不对称反应是目前有机化学研究的热点之一。本文综述了氮杂半冠醚手性配体与金属有机试剂络合的双金属催化剂,在催化不对称aldol反应、不对称Henry反应、不对称Michael反应、不对称Mannich反应、不对称Friedel-Crafts烷基化反应、不对称炔基化反应、不对称硅氰化反应、共聚反应、去对称化反应以及不对称Nozaki-Hiyama烯丙基化反应体系中的应用进展,重点介绍了不同催化体系对催化剂和反应底物之间立体效应和电子效应的影响,总结了控制反应立体选择性的规律以及有关催化反应的机理。
Bifunctional chiral metal complexes catalyzed asymmetric reactions are currently one of the hot topics in organic chemistry. In this paper, the bimetallic catalysts complexed with aza-semicyclic crown chiral ligands and metal-organic reagents are reviewed. In the catalytic asymmetric aldol reaction, asymmetric Henry reaction, asymmetric Michael reaction, asymmetric Mannich reaction, asymmetric Friedel-Crafts Alkylation, asymmetric alkynylation, asymmetric silanization, copolymerization, de-symmetric reactions, and asymmetric Nozaki-Hiyama allylation reaction systems are reviewed, with emphasis on the different catalytic systems The effect of the stereoscopic effect and the electronic effect between the catalyst and the reaction substrate, the rule of controlling the stereoselectivity of the reaction and the mechanism of the catalytic reaction are summarized.