Citation: Dongke Zhang, Li-Ao Ding, Qiuyu Xiang, Zhuojun Li, Qian Wu. P^Ⅲ/P^Ⅴ-catalytic platform enabling N-fluoro-thiocarbonylation of diaryl amines for modular synthesis of tertiary N-trifluoromethylamines[J]. Chinese Chemical Letters, ;2026, 37(5): 111461. doi: 10.1016/j.cclet.2025.111461 shu

P^Ⅲ/P^Ⅴ-catalytic platform enabling N-fluoro-thiocarbonylation of diaryl amines for modular synthesis of tertiary N-trifluoromethylamines

State Key Laboratory of Medicinal Chemical Biology, College of Pharmacy, Nankai University, Tianjin 300350, China

wuqian@nankai.edu.cn

Received Date: 2 April 2025
Revised Date: 6 June 2025
Accepted Date: 13 June 2025
Available Online: 14 June 2025

Figures(5)

Tertiary N–CF₃ compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF₃ derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a P^Ⅲ/P^Ⅴ redox catalyst, leading to the formation of series of diaryl N–CF₃ with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the P^Ⅲ/P^Ⅴ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
- N-Trifluoromethylation,
- Thiocarbamoyl fluoride,
- Silane,
- Phosphorus catalysis,
- Diaryl amine
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

PⅢ/PⅤ-catalytic platform enabling N-fluoro-thiocarbonylation of diaryl amines for modular synthesis of tertiary N-trifluoromethylamines

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通讯作者: 陈斌, bchen63@163.com

P^Ⅲ/P^Ⅴ-catalytic platform enabling N-fluoro-thiocarbonylation of diaryl amines for modular synthesis of tertiary N-trifluoromethylamines