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
1. [1]
  X.M. Zhang, Y.Q. Tu, F.M. Zhang, Z.H. Chen, S.H. Wang, Chem. Soc. Rev. 46 (2017) 2272–2305.
2. [2]
  R.R. Naredla, D.A. Klumpp, Chem. Rev. 113 (2013) 6905–6948. doi: 10.1021/cr4001385
3. [3]
  F.V. Singh, T. Wirth, Synthesis 45 (2013) 2499–2511. doi: 10.1055/s-0033-1339679
4. [4]
  B. Zhang, X. Li, B. Guo, Y. Du, Chem. Commun. 56 (2020) 14119–14136. doi: 10.1039/d0cc05354f
5. [5]
  S.E. Wengryniuk, S. Canesi, Rearrangements and Fragmentations Mediated by Hypervalent Iodine Reagents, PATAI’S Chemistry of Functional Groups, John Wiley & Sons, Ltd, Chichester, UK, 2018, pp. 665–706.
6. [6]
  Z. Yang, Y. Cheng, B. Zhang, et al., Chin. J. Org. Chem. 42 (2022) 3456–3505. doi: 10.6023/cjoc202206039
7. [7]
  A. Yoshimura, V.V. Zhdankin, Chem. Rev. 124 (2024) 11108–11186. doi: 10.1021/acs.chemrev.4c00303
8. [8]
  J. Qurban, M. Elsherbini, T. Wirth, J. Org. Chem. 82 (2017) 11872–11876. doi: 10.1021/acs.joc.7b01571
9. [9]
  C.B. Pandey, T. Azaz, R.S. Verma, M. Mishra, J.L. Jat, B. Tiwari, J. Org. Chem. 85 (2020) 10175–10181. doi: 10.1021/acs.joc.0c00347
10. [10]
  J. Zhang, A. Jalil, J. He, et al., Chem. Commun. 57 (2021) 7426–7429. doi: 10.1039/d1cc03110d
11. [11]
  Q. Wang, M. Biosca, F. Himo, K.J. Szabó, Angew. Chem. Int. Ed. 60 (2021) 26327–26331. doi: 10.1002/anie.202109461
12. [12]
  S. Manna, D. Aich, S. Hazra, S. Khandelwal, S. Panda, Chem. Sci. 15 (2024) 4989–4995. doi: 10.1039/d3sc06918d
13. [13]
  N. Okamoto, Y. Miwa, H. Minami, K. Takeda, R. Yanada, Angew. Chem. Int. Ed. 48 (2009) 9693–9696. doi: 10.1002/anie.200904960
14. [14]
  K. Miyamoto, Y. Sakai, S. Goda, M. Ochiai, Chem. Commun. 48 (2012) 982–984. doi: 10.1039/C2CC16360H
15. [15]
  A. Yoshimura, K.R. Middleton, M.W. Luedtke, C. Zhu, V.V. Zhdankin, J. Org. Chem. 77 (2012) 11399–11404. doi: 10.1021/jo302375m
16. [16]
  R. Oishi, K. Segi, H. Hamamoto, et al., Synlett 29 (2018) 1465–1468. doi: 10.1055/s-0037-1609686
17. [17]
  T. Maegawa, R. Oishi, A. Maekawa, et al., Synthesis 54 (2022) 4095–4103. doi: 10.1055/a-1835-2188
18. [18]
  X.Q. Li, W.K. Wang, C. Zhang, Adv. Synth. Catal. 351 (2009) 2342–2350. doi: 10.1002/adsc.200900428
19. [19]
  L.F. Silva, F.A. Siqueira, E.C. Pedrozo, F.Y.M. Vieira, A.C. Doriguetto, Org. Lett. 9 (2007) 1433–1436. doi: 10.1021/ol070027o
20. [20]
  M.S. Yusubov, G.A. Zholobova, I.L. Filimonova, K.W. Chi, Russ. Chem. Bull. Int. Ed. 53 (2004) 1735–1742. doi: 10.1007/s11172-005-0027-8
21. [21]
  M. Kameyama, F.A. Siqueira, M. Gracia-Mijares, L.F. Silva, M.T.A. Silva, Molecules 16 (2011) 9421–9438. doi: 10.3390/molecules16119421
22. [22]
  Y.C. Han, Y.D. Zhang, Q. Jia, J. Cui, C. Zhang, Org. Lett. 19 (2017) 5300–5303. doi: 10.1021/acs.orglett.7b02479
23. [23]
  L.F. Silva, Molecules 11 (2006) 421–434. doi: 10.3390/11060421
24. [24]
  L.F. Silva, R.S. Vasconcelos, M.A. Nogueira, Org. Lett. 10 (2008) 1017–1020. doi: 10.1021/ol800048f
25. [25]
  T. Abo, M. Sawaguchi, H. Senboku, S. Hara, Molecules 10 (2005) 183–189. doi: 10.3390/10010183
26. [26]
  J. Ren, F.H. Du, M.C. Jia, et al., Angew. Chem. Int. Ed. 60 (2021) 24171–24178. doi: 10.1002/anie.202108589
27. [27]
  W.W. Chen, A.B. Cuenca, A. Shafir, Angew. Chem. Int. Ed. 59 (2020) 16294–16309. doi: 10.1002/anie.201908418
28. [28]
  J. Tian, F. Luo, Q. Zhang, et al., J. Am. Chem. Soc. 142 (2020) 6884–6890. doi: 10.1021/jacs.0c00783
29. [29]
  W. Carpenter, J. Org. Chem. 31 (1966) 2688–2689. doi: 10.1021/jo01346a512
30. [30]
  N.O. Ilchenko, B.O.A. Tasch, K.J. Szabó, Angew. Chem. 126 (2014) 13111–13115. doi: 10.1002/ange.201408812
31. [31]
  G.C. Geary, E.G. Hope, A.M. Stuart, Angew. Chem. Int. Ed. 54 (2015) 14911–14914. doi: 10.1002/anie.201507790
32. [32]
  A. Andries-Ulmer, C. Brunner, J. Rehbein, T. Gulder, J. Am. Chem. Soc. 140 (2018) 13034–13041. doi: 10.1021/jacs.8b08350
33. [33]
  W.X. Lv, Q. Li, J.L. Li, et al., Angew. Chem. Int. Ed. 57 (2018) 16544–16548. doi: 10.1002/anie.201810204
34. [34]
  Z. Zhao, L. Racicot, G.K. Murphy, Angew. Chem. Int. Ed. 56 (2017) 11620–11623. doi: 10.1002/anie.201706798
35. [35]
  Z. Zhao, A.J. To, G.K. Murphy, Chem. Commun. 55 (2019) 14821–14824. doi: 10.1039/c9cc08310c
36. [36]
  E.V. Anslyn, D.A. Dougherty, Modern Physical Organic Chemistry, University Science Books, Sausalito, 2006, p. 658.
37. [37]
  K.B. Wiberg, P.R. Rablen, J. Org. Chem. 85 (2020) 11741–11749. doi: 10.1021/acs.joc.0c01469
38. [38]
  H.A. Sharma, K.M. Mennie, E.E. Kwan, E.N. Jacobsen, J. Am. Chem. Soc. 142 (2020) 16090–16096. doi: 10.1021/jacs.0c08150
39. [39]
  J. Ren, M.C. Jia, F.H. Du, C. Zhang, Chin. Chem. Lett. 33 (2022) 4834–4837. doi: 10.1016/j.cclet.2022.01.070
40. [40]
  J. Wu, L. Fu, R. Diao, et al., Green Synth. Catal. 6 (2025) 96–100.
41. [41]
  J. Fried, E.F. Sabo, J. Am. Chem. Soc. 76 (1954) 1455–1456. doi: 10.1021/ja01634a101
42. [42]
  P.M.A. Calverley, J.A. Anderson, B. Celli, et al., N. Engl. J. Med. 356 (2007) 775–789. doi: 10.1056/NEJMoa063070
43. [43]
  G.M. Keating, A. Vaidya, Drugs 74 (2014) 273–282. doi: 10.1007/s40265-014-0179-7
44. [44]
  B. Zhou, T. Yan, X.S. Xue, J.P. Cheng, Org. Lett. 18 (2016) 6128–6131. doi: 10.1021/acs.orglett.6b03134
45. [45]
  B. Zhou, X.S. Xue, J.P. Cheng, Tetrahedron Lett. 58 (2017) 1287–1291.
46. [46]
  M.W. Ha, S.M. Paek, Molecules 26 (2021) 4792. doi: 10.3390/molecules26164792
1. [1]
  Ya Ren , Cong Zhang , Haiyan Wang , Jin-Xia Liang , Chun Zhu , Han-Shi Hu , Jun Li . Defective Ru1@Mo2COx Single-Atom Catalyst for Efﬁcient Thermal Catalysis for Ammonia Synthesis. Chinese Journal of Structural Chemistry, 2025, 44(8): 100649-100649. doi: 10.1016/j.cjsc.2025.100649
2. [2]
  Tsegaye Tadesse Tsega , Jiantao Zai , Chin Wei Lai , Xin-Hao Li , Xuefeng Qian . Earth-abundant CuFeS2 nanocrystals@graphite felt electrode for high performance aqueous polysulfide/iodide redox flow batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100192-100192. doi: 10.1016/j.cjsc.2023.100192
3. [3]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-0. doi: 10.3866/PKU.WHXB202312010
4. [4]
  Rohit Kumar , Anita Sudhaik , Aftab Asalam Pawaz Khan , Van Huy Neguyen , Archana Singh , Pardeep Singh , Sourbh Thakur , Pankaj Raizada . Designing tandem S-scheme photo-catalytic systems: Mechanistic insights, characterization techniques, and applications. Acta Physico-Chimica Sinica, 2025, 41(11): 100150-0. doi: 10.1016/j.actphy.2025.100150
5. [5]
  Honglin Chen , Rupeng Wang , Zixiang He , Shih-Hsin Ho . Data-driven insights into nonradical activation mechanisms for biochar inverse design: A synergistic approach using DFT and machine learning with meta-analysis. Chinese Chemical Letters, 2026, 37(2): 111372-. doi: 10.1016/j.cclet.2025.111372
6. [6]
  Chunyan Yang , Qiuyu Rong , Fengyin Shi , Menghan Cao , Guie Li , Yanjun Xin , Wen Zhang , Guangshan Zhang . Rationally designed S-scheme heterojunction of BiOCl/g-C₃N₄ for photodegradation of sulfamerazine: Mechanism insights, degradation pathways and DFT calculation. Chinese Chemical Letters, 2024, 35(12): 109767-. doi: 10.1016/j.cclet.2024.109767
7. [7]
  Yanye Fan , Jingjing Chen , Bichun Chen , Jinyu Bai , Bowen Yang , Feng Liang , Lijing Fang . Design, synthesis and biological evaluation of Leu₁₀-teixobactin analogues. Chinese Chemical Letters, 2025, 36(4): 110075-. doi: 10.1016/j.cclet.2024.110075
8. [8]
  Run-Han Li , Tian-Yi Dang , Wei Guan , Jiang Liu , Ya-Qian Lan , Zhong-Min Su . Evolution exploration and structure prediction of Keggin-type group IVB metal-oxo clusters. Chinese Chemical Letters, 2024, 35(5): 108805-. doi: 10.1016/j.cclet.2023.108805
9. [9]
  Chaozheng He , Jia Wang , Ling Fu , Wei Wei . Nitric oxide assists nitrogen reduction reaction on 2D MBene: A theoretical study. Chinese Chemical Letters, 2024, 35(5): 109037-. doi: 10.1016/j.cclet.2023.109037
10. [10]
  Ting-Ting Huang , Jin-Fa Chen , Juan Liu , Tai-Bao Wei , Hong Yao , Bingbing Shi , Qi Lin . A novel fused bi-macrocyclic host for sensitive detection of Cr₂O₇²⁻ based on enrichment effect. Chinese Chemical Letters, 2024, 35(7): 109281-. doi: 10.1016/j.cclet.2023.109281
11. [11]
  Sanmei Wang , Yong Zhou , Hengxin Fang , Chunyang Nie , Chang Q Sun , Biao Wang . Constant-potential simulation of electrocatalytic N₂ reduction over atomic metal-N-graphene catalysts. Chinese Chemical Letters, 2025, 36(3): 110476-. doi: 10.1016/j.cclet.2024.110476
12. [12]
  Sanmei Wang , Dengxin Yan , Wenhua Zhang , Liangbing Wang . Graphene-supported isolated platinum atoms and platinum dimers for CO₂ hydrogenation: Catalytic activity and selectivity variations. Chinese Chemical Letters, 2025, 36(4): 110611-. doi: 10.1016/j.cclet.2024.110611
13. [13]
  Chen Chen , Jinzhou Zheng , Chaoqin Chu , Qinkun Xiao , Chaozheng He , Xi Fu . An effective method for generating crystal structures based on the variational autoencoder and the diffusion model. Chinese Chemical Letters, 2025, 36(4): 109739-. doi: 10.1016/j.cclet.2024.109739
14. [14]
  Wenzheng Chen , Weiyun Chen , Bin Chen , Mingbao Feng . Deciphering the electron-shuttling role of iron(Ⅲ) porphyrin in modulating the reductive UV/S(Ⅳ) system into the oxidative strategy for micropollutant abatement. Chinese Chemical Letters, 2025, 36(10): 110743-. doi: 10.1016/j.cclet.2024.110743
15. [15]
  Yu Su , Jinbo Hu , Laiqiang Xu , Xinwen Jiang , Gonggang Liu , Yuanjuan Bai , Yuanyuan Liao , Shanshan Chang , Xiaowei Cheng . Tannin-derived sulfur-doped carbon with tunable porosity and dilated interlayer spacing for reversible Na-ion diffusion. Chinese Chemical Letters, 2026, 37(2): 111210-. doi: 10.1016/j.cclet.2025.111210
16. [16]
  Vanita Vanita , Roland Schoch , Pascal Puphal , Hasan Yilmaz , Matthias Bauer , Oliver Clemens . Structural and electrochemical behaviour of bilayer manganite LaSr₂Mn₂O_6.96 cathode for all-solid-state fluoride ion batteries. Acta Physico-Chimica Sinica, 2026, 42(3): 100181-0. doi: 10.1016/j.actphy.2025.100181
17. [17]
  Yu Mao , Yilin Liu , Xiaochen Wang , Shengyang Ni , Yi Pan , Yi Wang . Acylfluorination of enynes via phosphine and silver catalysis. Chinese Chemical Letters, 2024, 35(8): 109443-. doi: 10.1016/j.cclet.2023.109443
18. [18]
  Zhiwei Zhong , Yanbin Huang , Wantai Yang . A simple photochemical method for surface fluorination using perfluoroketones. Chinese Chemical Letters, 2024, 35(5): 109339-. doi: 10.1016/j.cclet.2023.109339
19. [19]
  Chonglong He , Yulong Wang , Quan-Xin Li , Zichen Yan , Keyuan Zhang , Shao-Fei Ni , Xin-Hua Duan , Le Liu . Alkylarylation of alkenes with arylsulfonylacetate as bifunctional reagent via photoredox radical addition/Smiles rearrangement cascade. Chinese Chemical Letters, 2025, 36(5): 110253-. doi: 10.1016/j.cclet.2024.110253
20. [20]
  Xinwan Zhao , Yue Cao , Minjun Lei , Zhiliang Jin , Tsubaki Noritatsu . Constructing S-scheme heterojunctions by integrating covalent organic frameworks with transition metal sulfides for efficient noble-metal-free photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2025, 41(12): 100152-0. doi: 10.1016/j.actphy.2025.100152

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(17)
HTML views(3)

通讯作者: 陈斌, bchen63@163.com

1.
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

Metrics

通讯作者: 陈斌, bchen63@163.com

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