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NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl-alkyl cross-coupling.NHC与亲核试剂对烷基-烷基交叉偶联中活性铁(II)物种的螯合作用。
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2
The N-Methylpyrrolidone (NMP) Effect in Iron-Catalyzed Cross-Coupling with Simple Ferric Salts and MeMgBr.N-甲基吡咯烷酮(NMP)在简单铁盐和 MeMgBr 催化的铁催化交叉偶联中的作用。
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3
A Physical-Inorganic Approach for the Elucidation of Active Iron Species and Mechanism in Iron-Catalyzed Cross-Coupling.一种用于阐明铁催化交叉偶联中活性铁物种及机理的物理-无机方法。
Isr J Chem. 2017 Dec;57(12):1106-1116. doi: 10.1002/ijch.201700036. Epub 2017 Aug 24.
4
Elucidating the structure of a high-spin σ-phenyliron(iii) species in a live FeCl-PhZnCl reaction system.解析活性FeCl-PhZnCl反应体系中高自旋σ-苯基铁(III)物种的结构。
Chem Commun (Camb). 2018 Feb 11;54(12):1481-1484. doi: 10.1039/c7cc09737a. Epub 2018 Jan 23.
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J Am Chem Soc. 2017 Nov 15;139(45):16126-16133. doi: 10.1021/jacs.7b06377. Epub 2017 Nov 2.
6
DFT and AFIR Study on the Mechanism and the Origin of Enantioselectivity in Iron-Catalyzed Cross-Coupling Reactions.密度泛函理论(DFT)和原子力诱导反应(AFIR)研究铁催化交叉偶联反应的对映选择性机制和起源。
J Am Chem Soc. 2017 Nov 15;139(45):16117-16125. doi: 10.1021/jacs.7b05917. Epub 2017 Nov 2.
7
Intermediates and Reactivity in Iron-Catalyzed Cross-Couplings of Alkynyl Grignards with Alkyl Halides.铁催化炔基格氏试剂与烷基卤化物的交叉偶联反应中的中间体和反应性。
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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion.有机合成中的铁催化:对使这种贱金属成为多面手所需条件的批判性评估。
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Isolation, Characterization, and Reactivity of Fe8Me12(-): Kochi's S = 1/2 Species in Iron-Catalyzed Cross-Couplings with MeMgBr and Ferric Salts.Fe8Me12(-)的分离、表征及与 MeMgBr 和铁盐的铁催化交叉偶联反应中的活性:Kochi 的 S = 1/2 物种。
J Am Chem Soc. 2016 Jun 22;138(24):7492-5. doi: 10.1021/jacs.6b03760. Epub 2016 Jun 7.
10
Iron(II) Active Species in Iron-Bisphosphine Catalyzed Kumada and Suzuki-Miyaura Cross-Couplings of Phenyl Nucleophiles and Secondary Alkyl Halides.铁-双膦催化的苯基亲核试剂与仲烷基卤化物的熊田和铃木-宫浦交叉偶联反应中的亚铁活性物种
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铁催化交叉偶联反应中的中间体和机理。

Intermediates and Mechanism in Iron-Catalyzed Cross-Coupling.

机构信息

Department of Chemistry , University of Rochester , Rochester , New York 14627 , United States.

出版信息

J Am Chem Soc. 2018 Sep 26;140(38):11872-11883. doi: 10.1021/jacs.8b06893. Epub 2018 Sep 18.

DOI:10.1021/jacs.8b06893
PMID:30226380
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6217991/
Abstract

Iron-catalyzed cross-coupling reactions have attracted significant research interest, as they offer numerous favorable features compared with cross-coupling reactions with precious metal catalysis. While this research has contributed to an empirical understanding of iron-catalyzed cross-coupling, the underlying fundamental mechanisms of reaction and structures of catalytically active species have remained poorly defined. The lack of such detail can be attributed to the difficulties associated with studying such iron-catalyzed reactions, where unstable paramagnetic intermediates abound. Recently, the combined application of physical-inorganic spectroscopic methods, concomitant organic product analysis, and air- and temperature-sensitive inorganic synthesis has yielded the most detailed insight currently available on reactivity and mechanism in iron-catalyzed cross-coupling. This Perspective highlights this approach and the limitations of the contributing techniques as well as some of the key features of the catalytic reactions studied and lessons learned.

摘要

铁催化交叉偶联反应引起了广泛的研究兴趣,因为它们与贵金属催化的交叉偶联反应相比具有许多优势。虽然这项研究对铁催化交叉偶联反应的经验理解做出了贡献,但反应的基本机制和催化活性物质的结构仍然没有得到很好的定义。缺乏这些细节可以归因于研究此类铁催化反应的困难,其中大量存在不稳定的顺磁中间体。最近,物理无机光谱方法的联合应用、伴随的有机产物分析以及对空气和温度敏感的无机合成,为目前在铁催化交叉偶联中的反应性和机制方面提供了最详细的见解。本观点强调了这种方法以及贡献技术的局限性,以及研究的催化反应的一些关键特征和经验教训。