Citation: Boqiang Wang, Yongzhuo Xu, Jiajia Wang, Muyang Yang, Guo-Jun Deng, Wen Shao. Transition-metal free trifluoromethylimination of alkenes enabled by direct activation of N-unprotected ketimines[J]. Chinese Chemical Letters, ;2024, 35(9): 109502. doi: 10.1016/j.cclet.2024.109502 shu

Transition-metal free trifluoromethylimination of alkenes enabled by direct activation of N-unprotected ketimines

Boqiang Wang ^{a, 1} ,
Yongzhuo Xu ^{a, 1} ,
Jiajia Wang ^{a, *,} ,
Muyang Yang ^a ,
Guo-Jun Deng ^{a, b, *,} ,
Wen Shao ^{a, *,}

a.
Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China
b.
Department School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China

wangjiajia@xtu.edu.cn

gjdeng@xtu.edu.cn

shaowen@xtu.edu.cn

Received Date: 18 September 2023
Revised Date: 27 December 2023
Accepted Date: 4 January 2024
Available Online: 10 January 2024

Figures(5)

A highly site-selective intermolecular trifluoromethylimination of activated and unactivated olefins was reported under transition-metal- and photosensitizer-free conditions. This newly developed strategy provides straightforward and efficient access to diverse value-added vicinal trifluoromethyl amines without resorting to the pre-functionalized reagents. Mechanistic experiments demonstrate that the approach proceeded through CF₃ and iminyl two-radicals process, which were generated directly from commercially available benzophenone imine in a novel electron-donor mode via a SET process activated by the bifunctional hypervalent iodine reagents. The synthetic potential of the protocols was further showcased via the condensation/amination sequential cascade, and transformations to access β-CF₃ primary amines.
- Transition-metal free,
- Alkenes difunctionalization,
- Amination,
- Trifluoromethylation,
- Single-electron transfer
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