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由配体协同作用导向的钌（II）-氮杂环卡宾-二胺前催化剂的设计：不对称氢化反应的应用与机理研究

Design of Ru(II)-NHC-Diamine Precatalysts Directed by Ligand Cooperation: Applications and Mechanistic Investigations for Asymmetric Hydrogenation.

作者信息

Li Wei, Wagener Tobias, Hellmann Lars, Daniliuc Constantin G, Mück-Lichtenfeld Christian, Neugebauer Johannes, Glorius Frank

机构信息

Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, 48149 Münster, Germany.

出版信息

J Am Chem Soc. 2020 Apr 15;142(15):7100-7107. doi: 10.1021/jacs.0c00985. Epub 2020 Apr 1.

DOI:10.1021/jacs.0c00985
PMID:32195584
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7168601/
Abstract

A modular synthesis of Ru(II)-NHC-diamine complexes from readily available chiral N-heterocyclic carbenes (NHCs) and chiral diamines is disclosed for the first time. The well-defined Ru(II)-NHC-diamine complexes show unique structure and coordination chemistry including an unusual tridentate coordination effect of 1,2-diphenylethylenediamine. The isolated air- and moisture-stable Ru(II)-NHC-diamine complexes act as versatile precatalysts for the asymmetric hydrogenation of isocoumarines, benzothiophene 1,1-dioxides, and ketones. Moreover, on the basis of the identification of reaction intermediates by stoichiometric reactions and NMR experiments, together with the DFT calculations, a possible catalytic cycle was proposed.

摘要

首次公开了一种由易于获得的手性 N-杂环卡宾（NHCs）和手性二胺模块化合成 Ru(II)-NHC-二胺配合物的方法。结构明确的 Ru(II)-NHC-二胺配合物展现出独特的结构和配位化学，包括 1,2-二苯基乙二胺不同寻常的三齿配位效应。分离得到的对空气和湿气稳定的 Ru(II)-NHC-二胺配合物，可作为异香豆素、苯并噻吩 1,1-二氧化物和酮不对称氢化反应的通用前催化剂。此外，基于通过化学计量反应和 NMR 实验对反应中间体的鉴定，结合 DFT 计算，提出了一个可能的催化循环。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/babf/7168601/9cf0731d0722/ja0c00985_0008.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/babf/7168601/9cf0731d0722/ja0c00985_0008.jpg

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