手性铱(钌)配合物在不对称催化反应中的应用进展  

Advancements in asymmetric catalysis employing chiral iridium(ruthenium)complexes

作　　者：乔科 李彦霖 黄胜利 杨国昱 QIAO Ke;LI Yanlin;HUANG Shengli;YANG Guoyu(College of Chemistry and Chemical Industry,Beijing Institute of Technology,Beijing 102488,China;China ENFI Engineering Corporation,Beijing 100038,China)

机构地区：[1]北京理工大学化学与化工学院,北京102488 [2]中国恩菲工程技术有限公司,北京100038

出　　处：《无机化学学报》2024年第11期2091-2104,共14页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21971011)资助。

摘　　要：近年来,将手性八面体金属配合物用于不对称催化引起科学家们的广泛关注。手性八面体金属配合物根据配体是否具有手性可划分为手性仅来源于金属中心及手性来源于手性配体和金属中心的八面体金属配合物。本文介绍并归纳了手性环金属铱(Ir)和钌(Ru)配合物的设计与合成方法,即通过改变金属中心、配体的结合以及配体构型等对其进行调控。随后详细阐述了其在不对称催化中的应用,并根据催化方式不同将应用分为金属配位催化和配体球调控催化。金属配位催化包括多种有机不对称催化,以及可见光诱导多功能催化剂协同不对称催化。配体球调控催化主要用于烯烃加成反应。最后对手性八面体配合物作为配位超分子的建筑单元及其在不对称催化中的应用进行了展望,将二者优势结合有望实现更广泛的应用前景。Developing asymmetric catalysts derived solely from octahedral centrochirality has garnered significant attention in the scientific community.Chiral-octahedral metal complexes can be classified into stereogenic-only-at-metal complexes and stereogenic-at-metal complexes with chiral ligands.This review introduces the design and syn-thesis of chiral-octahedral iridium and ruthenium complexes,which can be fine-tuned by altering the metal center,ligand combinations,and the chirality or achirality of the ligands.The applications of these complexes in asymmet-ric catalysis are then explored,considering catalysis via metal binding and catalysis via the ligand sphere.Addition-ally,the potential of using octahedral chiral metal complexes as building units for supramolecular structures and their integration with asymmetric catalysis are discussed,suggesting promising perspectives for broader applications.

关 键 词：手性 不对称催化 环金属铱 吡啶钌(Ⅱ) 

分 类 号：O614.825[理学—无机化学] O614.821[理学—化学] O643.3