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钴催化羧酸的电还原胺化反应。

Electroreductive amination of carboxylic acids by cobalt catalysis.

作者信息

Bi Huihua, Chen Zhizheng, Bi Changsheng, Qu Shuanglin, Liu Jie

机构信息

College of Chemistry and Chemical Engineering, State Key Laboratory of Chemo and Biosensing, Hunan University, Changsha, China.

Greater Bay Area Institute for Innovation, Hunan University, Guangzhou, China.

出版信息

Nat Commun. 2025 Aug 4;16(1):7167. doi: 10.1038/s41467-025-62396-4.

DOI:10.1038/s41467-025-62396-4
PMID:40759900
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12322302/
Abstract

Catalytic reduction of carboxylic acids to valuable chemicals is highly desirable yet challenging for both biomass conversion and organic synthesis. Here we describe an efficient and sustainable electrocatalytic hydrogenation of carboxylic acids with amines utilizing protons as the hydrogen source. The application of an earth-abundant cobalt complex enables electrochemical generation of a cobalt-hydride intermediate, which serves as the key catalytically active species for this reductive process. Obviating the need for flammable H gas or sensitive hydrides, this general hydrogenative coupling of carboxylic acids with amines and nitroarenes allows producing a wide range of structurally diverse complex alkylamines under mild electrocatalytic conditions. Furthermore, the practicality and versatility of this protocol are demonstrated through its application in valuable isotope labeling using readily available deuterium sources.

摘要

将羧酸催化还原为有价值的化学品对于生物质转化和有机合成而言都非常有必要,但也具有挑战性。在此,我们描述了一种高效且可持续的方法,即利用质子作为氢源,通过电化学催化实现羧酸与胺的氢化反应。使用储量丰富的钴配合物能够实现电化学生成钴氢中间体,该中间体是此还原过程的关键催化活性物种。这种方法无需使用易燃的氢气或敏感的氢化物,通过羧酸与胺及硝基芳烃之间的这种通用氢化偶联反应,能够在温和的电催化条件下制备出结构多样的复杂烷基胺。此外,通过使用易于获得的氘源将该方法应用于有价值的同位素标记,证明了其实用性和通用性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/13b3504e3325/41467_2025_62396_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/a4ca38e40742/41467_2025_62396_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/d9e3772035a8/41467_2025_62396_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/67ff0dbb0fdf/41467_2025_62396_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/dfc15acd9135/41467_2025_62396_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/cc741937ff00/41467_2025_62396_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/13b3504e3325/41467_2025_62396_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/a4ca38e40742/41467_2025_62396_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/d9e3772035a8/41467_2025_62396_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/67ff0dbb0fdf/41467_2025_62396_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/dfc15acd9135/41467_2025_62396_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/cc741937ff00/41467_2025_62396_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e35f/12322302/13b3504e3325/41467_2025_62396_Fig6_HTML.jpg

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本文引用的文献

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Angew Chem Int Ed Engl. 2025 Mar 17;64(12):e202422742. doi: 10.1002/anie.202422742. Epub 2024 Dec 19.
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The Global Threat from the Irreversible Accumulation of Trifluoroacetic Acid (TFA).三氟乙酸(TFA)的不可逆转积累对全球构成的威胁。
Environ Sci Technol. 2024 Nov 12;58(45):19925-19935. doi: 10.1021/acs.est.4c06189. Epub 2024 Oct 30.
3
Electroreductive alkylations of (hetero)arenes with carboxylic acids.
(杂)芳烃与羧酸的电还原烷基化反应
Nat Commun. 2024 Jun 11;15(1):4970. doi: 10.1038/s41467-024-49355-1.
4
Electrohydrogenation of Nitriles with Amines by Cobalt Catalysis.钴催化下腈与胺的电氢化反应
Angew Chem Int Ed Engl. 2024 Feb 12;63(7):e202316140. doi: 10.1002/anie.202316140. Epub 2024 Jan 10.
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Comprehensive Comparisons between Directing and Alternating Current Electrolysis in Organic Synthesis.有机合成中直流电电解与交流电电解的综合比较
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