Citation: Peng Wang, Jianjun Wang, Ni Song, Xin Zhou, Ming Li. Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF₃·OEt₂-catalyzed C‒F bond activation[J]. Chinese Chemical Letters, ;2025, 36(1): 109748. doi: 10.1016/j.cclet.2024.109748 shu

Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF₃·OEt₂-catalyzed C‒F bond activation

Peng Wang ^a ,
Jianjun Wang ^a ,
Ni Song ^{a, b} ,
Xin Zhou ^{a, *,} ,
Ming Li ^{a, b, *,}

a.
Molecular Synthesis Center, Key Laboratory of Marine Medicine, Chinese Ministry of Education, School of Medicine and Pharmacy, Ocean University of China, Qingdao 266003, China
b.
Laboratory for Marine Drugs and Bioproducts, Pilot National Laboratory for Marine Science and Technology, Qingdao 266237, China

zhouxin0@qibebt.ac.cn

lmsnouc@ouc.edu.cn

Received Date: 18 October 2023
Revised Date: 23 February 2024
Accepted Date: 5 March 2024
Available Online: 8 March 2024

Figures(4)

Ag₂CO₃-promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source. The reaction involves β-fragmentation of primary alkoxy radicals, followed by the fluorination of the resulting C-centered radical intermediates. The transformation proceeds under mild reaction conditions and exhibits a broad substrate scope, thus opening up a new entrance to the synthesis of fluorinated constructs including α-fluoroimides and 1-fluoroalkyl benzoates as well as secondary and tertiary alkyl fluorides like versatile 2-fluoro-2-alkyl 1,3-propandiol derivatives. The divergent functionalization of the obtained α-fluoroimides enables an efficient access to amine derivatives through C–F bond activation under the action of BF₃·OEt₂.
- Dehydroxymethylative fluorination,
- Alkoxy radicals,
- β-Fragmentation,
- Silver catalysis,
- C–F Bond activation
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Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF3·OEt2-catalyzed C‒F bond activation

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通讯作者: 陈斌, bchen63@163.com

Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF₃·OEt₂-catalyzed C‒F bond activation