Citation: Yang Li, Yanan Dong, Zhihong Wei, Changzeng Yan, Zhen Li, Lin He, Yuehui Li. Fluoride-promoted Ni-catalyzed cyanation of C–O bond using CO₂ and NH₃[J]. Chinese Chemical Letters, ;2025, 36(5): 110206. doi: 10.1016/j.cclet.2024.110206 shu

Fluoride-promoted Ni-catalyzed cyanation of C–O bond using CO₂ and NH₃

Yang Li ^{a, b} ,
Yanan Dong ^{a, *,} ,
Zhihong Wei ^c ,
Changzeng Yan ^d ,
Zhen Li ^a ,
Lin He ^{a, *,} ,
Yuehui Li ^{a, d, *,}

a.
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
Institute of Molecular Science, Shanxi University, Taiyuan 030006, China
d.
College of Smart Energy, Shanghai Jiao Tong University, Shanghai 200240, China

dongyanan@sjtu.edu.cn

helin@licp.cas.cn

liyuehui@sjtu.edu.cn

Received Date: 12 May 2024
Revised Date: 26 June 2024
Accepted Date: 2 July 2024
Available Online: 2 July 2024

Figures(9)

The selective conversion of CO₂ and NH₃ into valuable nitriles presents significant potential for CO₂ utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO₂ and NH₃ as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
- Fluoride-promoted,
- CO₂ utilization,
- Cyanation,
- Hydrosilane,
- Nickel-catalyzed
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沈阳化工大学材料科学与工程学院沈阳 110142

Fluoride-promoted Ni-catalyzed cyanation of C–O bond using CO2 and NH3

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通讯作者: 陈斌, bchen63@163.com

Fluoride-promoted Ni-catalyzed cyanation of C–O bond using CO₂ and NH₃