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在室温下使用碱金属卤化物/Fe(NO)₃·9H₂O对芳烃进行卤化反应。

Halogenation of arenes using alkali metal halides/Fe(NO)·9HO at room temperature.

作者信息

Li Caicui, Cheng Yao, Pang Fudan, Yan Xiushuo, Huang Zhengtao, Wang Xinmei, Wang Xiaodan, Li Yiying, Wang Jinhui, Xu Huanjun

机构信息

Department of Medicinal Chemistry and Natural Medicine Chemistry, College of Pharmacy, Harbin Medical University Harbin China

School of Science, Qiongtai Normal University Haikou 571127 China

出版信息

RSC Adv. 2025 Mar 19;15(11):8523-8528. doi: 10.1039/d5ra00837a. eCollection 2025 Mar 17.

DOI:10.1039/d5ra00837a
PMID:40109924
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11920861/
Abstract

A simple, efficient and environmentally friendly methodology for the halodecarboxylation of anisole analogues using Fe(NO)·9HO/KBr or NaI at room temperature was developed. In this method, most substrates with an electron-donating group afforded corresponding products in good to excellent yields, whereas those with an electron-withdrawing group afforded low to moderate yields. More importantly, this protocol was also applicable for gram-scale synthesis. It is hoped that this methodology will be highly useful in organic synthesis.

摘要

开发了一种简单、高效且环境友好的方法,用于在室温下使用Fe(NO)₃·9H₂O/KBr或NaI对苯甲醚类似物进行卤代脱羧反应。在该方法中,大多数带有供电子基团的底物能以良好至优异的产率得到相应产物,而那些带有吸电子基团的底物产率则较低至中等。更重要的是,该方案也适用于克级规模的合成。希望这种方法在有机合成中会非常有用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3bd9/11920861/56a4649c13de/d5ra00837a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3bd9/11920861/b088a7505c9f/d5ra00837a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3bd9/11920861/56a4649c13de/d5ra00837a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3bd9/11920861/b088a7505c9f/d5ra00837a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3bd9/11920861/56a4649c13de/d5ra00837a-s2.jpg

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本文引用的文献

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Late-Stage C-H Nitration of Unactivated Arenes by Fe(NO)·9HO in Hexafluoroisopropanol.Fe(NO)·9H₂O在六氟异丙醇中对未活化芳烃的后期C-H硝化反应
Org Lett. 2024 Apr 19;26(15):3316-3320. doi: 10.1021/acs.orglett.4c01006. Epub 2024 Apr 10.
2
Recent progress in the oxidative bromination of arenes and heteroarenes.芳环和杂芳环的氧化溴化研究进展。
Org Biomol Chem. 2023 Feb 22;21(8):1571-1590. doi: 10.1039/d3ob00019b.
3
Catalytic Oxidative Cleavage of C(OH)-C Bonds in Lignin Model Compounds to Carboxylic Acids by Fe(NO).9HO/NaI/DMSO.
Fe(NO)₃·9H₂O/NaI/二甲基亚砜催化木质素模型化合物中C(OH)-C键氧化裂解生成羧酸
Front Chem. 2022 Jul 1;10:933763. doi: 10.3389/fchem.2022.933763. eCollection 2022.
4
Substrate Controlled Regioselective Bromination of Acylated Pyrroles Using Tetrabutylammonium Tribromide (TBABr).使用四丁基三溴化铵(TBABr)对酰化吡咯进行底物控制的区域选择性溴化反应。
J Org Chem. 2018 Aug 17;83(16):9250-9255. doi: 10.1021/acs.joc.8b01251. Epub 2018 Jul 17.
5
Regioselective nitration of anilines with Fe(NO)·9HO as a promoter and a nitro source.以 Fe(NO)·9HO 为促进剂和硝基源对苯胺进行区域选择性硝化。
Org Biomol Chem. 2018 May 30;16(21):3881-3884. doi: 10.1039/c8ob00841h.
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Combining Eosin Y with Selectfluor: A Regioselective Brominating System for Para-Bromination of Aniline Derivatives.将曙红 Y 与 Selectfluor 结合:一种对苯胺衍生物进行对位溴化的区域选择性溴化体系。
Org Lett. 2017 Jul 21;19(14):3799-3802. doi: 10.1021/acs.orglett.7b01427. Epub 2017 Jun 29.
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Computational Investigation of the Role Played by Rhodium(V) in the Rhodium(III)-Catalyzed ortho-Bromination of Arenes.铑(V)在铑(III)催化的芳烃邻位溴化反应中所起作用的计算研究
Chemistry. 2017 Feb 21;23(11):2690-2699. doi: 10.1002/chem.201605188. Epub 2017 Jan 26.
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