Citation: Fen Wu, Xin Li, Junbiao Chang, Dachang Bai. Palladium-catalyzed multi components oxy-aminofluorination and aminofluorination of gem-difluoroalkenes[J]. Chinese Chemical Letters, ;2024, 35(2): 109155. doi: 10.1016/j.cclet.2023.109155 shu

Palladium-catalyzed multi components oxy-aminofluorination and aminofluorination of gem-difluoroalkenes

Fen Wu ^a ,
Xin Li ^a ,
Junbiao Chang ^a ,
Dachang Bai ^{a, b, *,}

a.
State Key Laboratory of Antiviral Drugs, NMPA Key Laboratory for Research and Evaluation of Innovative Drug, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Pingyuan Laboratory, Henan Normal University, Xinxiang 453007, China
b.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

baidachang@htu.edu.cn

Received Date: 7 July 2023
Revised Date: 19 September 2023
Accepted Date: 25 September 2023
Available Online: 28 September 2023

Figures(7)

Organofluorine compounds are widely used in the realm of drug discovery and material science. Herein, we developed palladium catalyzed intermolecular aminofluorination and oxy-aminofluorination of gem-difluoroalkenes with N-fluorobenzenesulfonimide (NFSI), in which NFSI was used as the nitrogen source and oxidant. The reaction provides an efficient and straightforward synthesis route of a series of α-trifluoromethyl benzylic amines. Notably, three/four components oxy-aminofluorination processes were realized to give α-trifluoromethyl benzylic ether with a terminal amino group, which proceed through C(sp³)–O bond cleavage of easily available ether and simultaneous introduced a fluorine, an amino and an oxy substituent in one pot with excellent regioselectivity. The divergent reactivity not only included the incorporation of one ether molecular, but also much more challenged two ether insertion with excellent selectivity through succession C(sp³)–O bonds cleavage. This protocol allows for concise synthesis of high value amines with fluoroalkyl-substituents and selectively transformation of easily available ethers by high-valent palladium catalysis.
- Palladium,
- Multi components,
- Aminofluorination,
- Oxy-aminofluorination,
- C(sp³)–O bond cleavage
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