Citation: Shunyao Tang, Siyi Wang, Dongmei Zhang, Xinxing Zhang, Guang Yang, Yanwei Wang, Youai Qiu. Selective nickel-electrocatalyzed benzylic C–H oxygenation of functionalized alkyl arenes[J]. Chinese Chemical Letters, ;2024, 35(2): 108660. doi: 10.1016/j.cclet.2023.108660 shu

Selective nickel-electrocatalyzed benzylic C–H oxygenation of functionalized alkyl arenes

Shunyao Tang ^a ,
Siyi Wang ^a ,
Dongmei Zhang ^b ,
Xinxing Zhang ^{b, *,} ,
Guang Yang ^a ,
Yanwei Wang ^a ,
Youai Qiu ^{a, *,}

a.
State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China
b.
College of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center (RECAST), Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China

zhangxx@nankai.edu.cn

qiuyouai@nankai.edu.cn

Received Date: 12 January 2023
Revised Date: 3 June 2023
Accepted Date: 6 June 2023
Available Online: 7 June 2023

Figures(5)

Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities, such as free carboxylic acid, aldehyde, halogen (including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp³)–H bonds, and short-lived reactive intermediates (aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode (BUME) with nano-electrospray ionization mass spectrometry.
- Electrochemical C–H oxidation,
- Functionalized alkyl arenes,
- Paired nickel-electrocatalysis,
- H₂O oxidation,
- Ketones
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