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铁催化交叉脱氢偶联反应

Iron-Catalyzed Cross-Dehydrogenative Coupling.

作者信息

Diao Haiyan, Chen Yujia, Liu Feng

机构信息

Department of Chemistry, Fudan University, Shanghai 200438, China.

School of Chemistry and Chemical Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China.

出版信息

Molecules. 2025 Jan 10;30(2):250. doi: 10.3390/molecules30020250.

DOI:10.3390/molecules30020250
PMID:39860120
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11767816/
Abstract

This review highlights significant advances in iron-catalyzed cross-dehydrogenative coupling (CDC), a method pivotal for forming carbon-carbon (C-C) bonds directly from C-H bonds. This technique uses iron-a naturally abundant, inexpensive, and environmentally benign transition metal-as a catalyst to facilitate the coupling of two unfunctionalized C-H bonds. This method stands out for avoiding pre-functionalized substrates, reducing both waste and cost in organic synthesis. The discussion includes a variety of CDC methodologies involving combinations of C(sp)-H with C(sp)-H, C(sp)-H with C(sp)-H, and C(sp)-H with C(sp)-H bonds. These methods have been successfully applied in synthesizing complex molecules and pharmaceuticals, highlighting the versatility and efficiency of iron catalysis.

摘要

本综述重点介绍了铁催化交叉脱氢偶联反应(CDC)的重大进展,该方法是直接由碳氢键形成碳-碳(C-C)键的关键方法。该技术使用铁——一种天然丰富、价格低廉且环境友好的过渡金属——作为催化剂,以促进两个未官能团化的碳氢键的偶联。该方法的突出之处在于避免了预官能团化的底物,减少了有机合成中的废物和成本。讨论内容包括多种CDC方法,涉及C(sp)-H与C(sp)-H、C(sp)-H与C(sp)-H以及C(sp)-H与C(sp)-H键的组合。这些方法已成功应用于合成复杂分子和药物,突出了铁催化的多功能性和效率。

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Iron-catalyzed tandem oxidative coupling and acetal hydrolysis reaction to prepare formylated benzothiazoles and isoquinolines.铁催化串联氧化偶联和缩醛水解反应制备甲酰化苯并噻唑和异喹啉。
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Iron-Catalyzed Tertiary Alkylation of Terminal Alkynes with 1,3-Diesters via a Functionalized Alkyl Radical.
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Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9706-9711. doi: 10.1002/anie.202100641. Epub 2021 Mar 12.
4
Organic synthesis with the most abundant transition metal-iron: from rust to multitasking catalysts.利用最丰富的过渡金属-铁进行有机合成:从铁锈到多功能催化剂。
Chem Soc Rev. 2021 Jan 7;50(1):243-472. doi: 10.1039/d0cs00688b. Epub 2021 Jan 5.
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Cross-Dehydrogenative Alkynylation: A Powerful Tool for the Synthesis of Internal Alkynes.交叉脱氢炔基化反应:一种构建内部炔烃的有力工具。
ChemSusChem. 2020 Sep 18;13(18):4776-4794. doi: 10.1002/cssc.202001165. Epub 2020 Aug 13.
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En Route to Intermolecular Cross-Dehydrogenative Coupling Reactions.通向分子间交叉脱氢偶联反应之路
J Org Chem. 2019 Oct 18;84(20):12705-12721. doi: 10.1021/acs.joc.9b01704. Epub 2019 Sep 6.
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Iron-Catalyzed Regioselective α-C-H Alkylation of N-Methylanilines: Cross-Dehydrogenative Coupling between Unactivated C(sp)-H and C(sp)-H Bonds via a Radical Process.铁催化N-甲基苯胺的区域选择性α-C-H烷基化反应:通过自由基过程实现未活化C(sp³)-H与C(sp³)-H键之间的交叉脱氢偶联反应
J Org Chem. 2019 Jun 7;84(11):6830-6839. doi: 10.1021/acs.joc.9b00625. Epub 2019 May 29.
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Iron Catalysis in Reduction and Hydrometalation Reactions.铁催化在还原和加氢金属化反应中的应用。
Chem Rev. 2019 Feb 27;119(4):2550-2610. doi: 10.1021/acs.chemrev.8b00372. Epub 2018 Dec 14.
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Iron Phosphate Catalyzed Asymmetric Cross-Dehydrogenative Coupling of 2-Naphthols with β-Ketoesters.铁磷酸盐催化的 2-萘酚与β-酮酸酯的不对称交叉脱氢偶联反应。
Org Lett. 2017 Jun 2;19(11):2917-2920. doi: 10.1021/acs.orglett.7b01152. Epub 2017 May 12.
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Iron-Catalyzed Dehydrogenative sp-sp Coupling via Direct Oxidative C-H Activation of Acetonitrile.铁催化的通过直接氧化腈 sp-sp 偶联脱氢 C-H 活化。
Org Lett. 2017 May 5;19(9):2226-2229. doi: 10.1021/acs.orglett.7b00678. Epub 2017 Apr 26.