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活化醇类稳定烷基自由基的电化学脱氧胺化反应。

Electrochemical deoxygenative amination of stabilized alkyl radicals from activated alcohols.

作者信息

Xu Jia, Liu Yilin, Wang Qing, Tao Xiangzhang, Ni Shengyang, Zhang Weigang, Yu Lei, Pan Yi, Wang Yi

机构信息

Jiangsu Key Laboratory of Advanced Organic Materials, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.

出版信息

Nat Commun. 2024 Jul 20;15(1):6116. doi: 10.1038/s41467-024-50596-3.

DOI:10.1038/s41467-024-50596-3
PMID:39033147
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11271281/
Abstract

Alkylamine structures represent one of the most functional and widely used in organic synthesis and drug design. However, the general methods for the functionalization of the shielded and deshielded alkyl radicals remain elusive. Here, we report a general deoxygenative amination protocol using alcohol-derived carbazates and nitrobenzene under electrochemical conditions. A range of primary, secondary, and tertiary alkylamines are obtained. This practical procedure can be scaled up through electrochemical continuous flow technique.

摘要

烷基胺结构是有机合成和药物设计中功能最多且应用最广泛的结构之一。然而,关于被保护和去保护的烷基自由基功能化的通用方法仍然未知。在此,我们报道了一种在电化学条件下使用醇衍生的氨基甲酸酯和硝基苯的通用脱氧胺化方法。可获得一系列伯、仲和叔烷基胺。这一实用方法可通过电化学连续流动技术进行放大。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/4e26e7f0346a/41467_2024_50596_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/ed4e6da9411e/41467_2024_50596_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/80744a0d6bc9/41467_2024_50596_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/92563b3075b5/41467_2024_50596_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/e25cc65d36d3/41467_2024_50596_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/4e26e7f0346a/41467_2024_50596_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/ed4e6da9411e/41467_2024_50596_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/80744a0d6bc9/41467_2024_50596_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/92563b3075b5/41467_2024_50596_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/e25cc65d36d3/41467_2024_50596_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/89f1/11271281/4e26e7f0346a/41467_2024_50596_Fig5_HTML.jpg

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本文引用的文献

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Electrochemical Nickel-Catalyzed C(sp)-C(sp) Cross-Coupling of Alkyl Halides with Alkyl Tosylates.电化学镍催化卤代烃与甲苯磺酸酯的C(sp)-C(sp)交叉偶联反应
J Am Chem Soc. 2023 Aug 9;145(31):17023-17028. doi: 10.1021/jacs.3c07313. Epub 2023 Jul 26.
2
Alkyl sulfinates as cross-coupling partners for programmable and stereospecific installation of C(sp) bioisosteres.烷基磺酸盐作为交叉偶联伙伴,用于可编程和立体特异性安装 C(sp) 生物等排体。
Nat Chem. 2023 Apr;15(4):550-559. doi: 10.1038/s41557-023-01150-z. Epub 2023 Mar 2.
3
Dehydroxylative Arylation of Alcohols via Paired Electrolysis.
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Org Lett. 2022 Oct 14;24(40):7476-7481. doi: 10.1021/acs.orglett.2c03136. Epub 2022 Oct 3.
4
Deoxytrifluoromethylation of Alcohols.醇的去氧三氟甲基化反应。
J Am Chem Soc. 2022 Jul 13;144(27):11961-11968. doi: 10.1021/jacs.2c04807. Epub 2022 Jul 5.
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Electrochemical Enantioselective Nucleophilic α-C(sp)-H Alkenylation of 2-Acyl Imidazoles.电化学手性亲核 α-C(sp 3 )-H 烯丙基化 2-酰基咪唑。
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