Citation: Jing Ren, Feng-Huan Du, Xiaowei Chen, Chi Zhang. Monofluoroiodane(Ⅲ) reagent mediated Wagner−Meerwein rearrangement fluorination: Construction of quaternary C(sp³)−F bond[J]. Chinese Chemical Letters, ;2026, 37(5): 111407. doi: 10.1016/j.cclet.2025.111407 shu

Monofluoroiodane(Ⅲ) reagent mediated Wagner−Meerwein rearrangement fluorination: Construction of quaternary C(sp³)−F bond

Jing Ren ^{a, b, 1,} ,
Feng-Huan Du ^{a, 1} ,
Xiaowei Chen ^a ,
Chi Zhang ^{a, *,}

a.
State Key Laboratory of Elemento-Organic Chemistry, The Research Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
b.
Shanxi Bethune Hospital, Shanxi Academy of Medical Sciences, Tongji Shanxi Hospital, Third Hospital of Shanxi Medical University, Taiyuan 030032, China

renjing1114@126.com

zhangchi@nankai.edu.cn

Received Date: 4 March 2025
Revised Date: 22 May 2025
Accepted Date: 3 June 2025
Available Online: 4 June 2025

Figures(10)

Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp³)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R¹ attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF₄ were understood by control experiments and density functional theory calculations.
- Monofluoroiodane(Ⅲ) reagent,
- Silver(Ⅰ)-catalysis,
- Wagner-Meerwein rearrangement,
- Fluorination,
- DFT
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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

Monofluoroiodane(Ⅲ) reagent mediated Wagner−Meerwein rearrangement fluorination: Construction of quaternary C(sp3)−F bond

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通讯作者: 陈斌, bchen63@163.com

Monofluoroiodane(Ⅲ) reagent mediated Wagner−Meerwein rearrangement fluorination: Construction of quaternary C(sp³)−F bond