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对映体纯——过渡金属配合物作为手性转移的有效工具

Enantiomerically Pure --Complexes of Transition Metals as an Effective Tool for Chirality Transfer.

作者信息

Kovyazin Pavel V, Khalilov Leonard M, Parfenova Lyudmila V

机构信息

Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences, 141 Prospekt Oktyabrya, 450075 Ufa, Russia.

出版信息

Molecules. 2025 Jun 8;30(12):2511. doi: 10.3390/molecules30122511.

Abstract

Chiral --complexes of transition metals have shown remarkable efficacy in organometallic synthesis and catalysis. Additionally, enantiomerically pure -complexes hold promise for the development of novel chiral materials and pharmaceuticals. The discovery and synthesis of a diverse range of group IVB and IIIB metal complexes represents a significant milestone in the advancement of stereoselective catalytic methods for constructing metal-C, C-C, C-H, and C-heteroatom bonds. The synthesis of enantiomerically pure metallocenes can be accomplished through several strategies: utilizing optically active precursors of -ligands, separation of diastereomers of complexes with enantiomerically pure agents, and synthesis via the stereocontrolled reactions of enantiomerically pure σ-complexes with prochiral anions of -ligands. This review focuses on the analysis of various nuances of the synthesis of enantiomerically pure --complexes of titanium and lanthanum families. Their applicability as effective catalysts in asymmetric carbomagnesiation, carbo- and cycloalumination, oligo- and polymerization, Diels-Alder cycloaddition, reactions of zirconaaziridines, cyclization, hydrosilylation, hydrogenation, hydroamination, and other processes are highlighted as well.

摘要

过渡金属的手性配合物在有机金属合成和催化中显示出显著的功效。此外,对映体纯的配合物有望用于开发新型手性材料和药物。发现和合成多种IVB族和IIIB族金属配合物是构建金属 - 碳、碳 - 碳、碳 - 氢和碳 - 杂原子键的立体选择性催化方法发展中的一个重要里程碑。对映体纯的茂金属的合成可以通过几种策略来实现:利用配体的旋光性前体、用对映体纯试剂分离配合物的非对映体以及通过对映体纯的σ - 配合物与配体的前手性阴离子的立体控制反应进行合成。本综述着重分析钛族和镧族对映体纯配合物合成的各种细微差别。还强调了它们作为有效催化剂在不对称碳镁化、碳铝化和环铝化、低聚和聚合、狄尔斯 - 阿尔德环加成、锆氮杂环丙烷反应、环化、硅氢化、氢化、氢胺化及其他过程中的适用性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7428/12195769/3b45d953d45b/molecules-30-02511-sch001.jpg

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