DOI: 10.1016/s0040-4039(02)00047-3. Electroorganic synthesis under solvent-free conditions. Highly regioselective anodic monofluorination of cyclic ethers, lactones, and a cyclic carbonate

Electroorganic synthesis under solvent-free conditions. Highly regioselective anodic monofluorination of cyclic ethers, lactones, and a cyclic carbonate

10.1016/s0040-4039(02)00047-3

Crossref journal-article

Elsevier BV

Tetrahedron Letters (78)

Bibliography

Hasegawa, M., Ishii, H., & Fuchigami, T. (2002). Electroorganic synthesis under solvent-free conditions. Highly regioselective anodic monofluorination of cyclic ethers, lactones, and a cyclic carbonate. Tetrahedron Letters, 43(8), 1503â1505.

Authors 3

Masaru Hasegawa (first)
Hideki Ishii (additional)
Toshio Fuchigami (additional)

References 17 Referenced 64

Electroorganic Reaction in Ionic Liquids. Part 1: Electrolytic Partial Fluorination of Organic Compounds. Part 58.
10.1149/1.2059336 / J. Electrochem. Soc. by Ue (1994)
{'key': '10.1016/S0040-4039(02)00047-3_BIB3', 'first-page': '1080', 'volume': '61', 'author': 'Ue', 'year': '1993', 'journal-title': 'Electrochemistry (formally Denki kagaku)'} / Electrochemistry (formally Denki kagaku) by Ue (1993)
10.1016/S0378-7753(98)00233-X / J. Power Sources by Katayama (1999)
10.1016/S0013-4686(99)00196-6 / Electrochim. Acta by Inaba (1999)
10.1021/jo00960a040 / J. Org. Chem. by Adcock (1973)
2-Fluoro-1,4-dioxane (4): colorless oil; 1H NMR (270 MHz, CDCl3) δ 5.39 (d, J=52 Hz, 1H), 4.24 (m, 1H), 3.90–3.71 (m, 5H); 13C NMR (67.8 MHz, CDCl3) δ 103.073 (d, J=221 Hz), 67.292 (d, J=25.7 Hz), 65.650, 60.671; 19F NMR (254 MHz, CDCl3) δ −61.1 (ddd, J=52, 35, 5.3 Hz); MS (m/z) 106 (M+), 87 (M+−F), 86, 73; HRMS m/z calcd for C4H7FO2: 106.0430. Found: 106.0483.
10.1016/0013-4686(93)80222-L / Electrochim. Acta by Momota (1993)
10.1246/cl.1994.849 / Chem. Lett. by Yoneda (1994)
A typical procedure for the anodic fluorination is as follows. Anodic fluorination of 1 (4.90 g, 68.0 mmol) was carried out at platinum electrodes (2×2 cm2) in 2.0 M Et4NF·4HF (1.5 equiv. of F− to 1, a total volume of 1 and Et4NF·4HF was 10 ml) in a cylindrical undivided cell under a nitrogen atmosphere at room temperature. Constant current (150 mA/cm2) was applied. After 2 F/mol of charge was passed, the corresponding fluorinated compound 2 (3.43 g, 38.1 mmol) was isolated by simple distillation of the electrolytic solution (bp 73°C).
2-Fluorotetrahydrofuran (2): colorless oil; 1H NMR (270 MHz, CDCl3) δ 5.88 (d, J=67 Hz, 1H), 4.26–4.14 (m, 1H), 4.02–3.91 (m, 1H), 2.35–1.65 (m, 4H); 13C NMR (67.8 MHz, CDCl3) δ 112.6769 (d, J=216 Hz), 69.414, 46.122, 33.172 (d, J=25.7 Hz), 21.719; 19F NMR (254 MHz, CDCl3) δ −34.8 (m); MS (m/z) 71 (M+−F), 69, 43; HRMS m/z calcd for C4H7O (M+−F): 71.0497. Found: 71.0487.
2-Fluoro-1,3-dioxolane (6): colorless oil; 1H NMR (270 MHz, CDCl3) δ 6.31 (d, J=92 Hz, 1H), 4.25–4.18 (m, 2H), 4.14–4.04 (m, 2H); 13C NMR (67.8 MHz, CDCl3) δ 117.209 (d, J=249 Hz), 63.153 (d, J=16.7 Hz); 19F NMR (254 MHz, CDCl3) δ −1.99 (d, J=92.5 Hz); MS (m/z) 73 (M+−F); HRMS m/z calcd for C3H5O2 (M+−F): 73.0290. Found: 73.0263.
5-Fluoro-5-pentanolide (8): colorless oil; 1H NMR (270 MHz, CDCl3) δ 6.20 (dd, J=62.3, 3.5 Hz, 1H), 2.82–2.63 (m, 1H), 2.57–2.32 (m, 3H); 13C NMR (67.8 MHz, CDCl3) δ 174.77 (d, J=3.9 Hz), 109.08 (d, J=229 Hz), 28.87 (d, J=24.6 Hz), 24.57; 19F NMR (254 MHz, CDCl3) δ −43.17 (br ddd, J=61.0, 27.7, 22.2 Hz); MS (m/z) 104 (M+), 85; HRMS m/z calcd for C4H5FO2: 104.0274. Found: 104.0219.
5-Fluoro-5-methyl-5-pentanolide (10): colorless oil; 1H NMR (270 MHz, CDCl3) δ 2.82 (ddd, J=18, 11, 9.1 Hz, 1H), 2.63–2.42 (m, 2H), 2.24 (dddd, J=32, 14, 11, 9.7 Hz, 1H), 1.76 (d, J=18 Hz, 3H); 13C NMR (67.8 MHz, CDCl3) δ 174.75 (d, J=1.7 Hz), 118.22 (d, J=226 Hz), 33.29 (d, J=28 Hz), 27.34, 23.48 (d, J=30 Hz); 19F NMR (254 MHz, CDCl3) δ −16.6 (ddq, J=31, 13, 19 Hz); MS (m/z) 118 (M+), 103, 99; HRMS m/z calcd for C5H7FO2: 118.0430. Found: 118.0431.
10.1016/S0022-1139(01)00343-8 / J. Fluorine Chem. by Sasaki (2001)
10.1039/b004652n / Chem. Commun. by Ishii (2000)
Kobayashi, M.; Inoguchi, T.; Yamashita, S.; Fukai, Y. In Proceedings of the International Conference on Fluorine Chemistry, Yokohama, Japan, 9–11 May, 1999; Abstr. No. P–14, p. 74.

Dates

Type	When
Created	22 years, 5 months ago (March 25, 2003, 8:14 p.m.)
Deposited	3 years, 2 months ago (June 24, 2022, 8:36 p.m.)
Indexed	2 weeks ago (Aug. 23, 2025, 12:58 a.m.)
Issued	23 years, 7 months ago (Feb. 1, 2002)
Published	23 years, 7 months ago (Feb. 1, 2002)
Published Print	23 years, 7 months ago (Feb. 1, 2002)

Funders 1

Ministry of Education, Culture, Sports, Science and Technology 10.13039/501100001700
Region: Asia
gov (National government)
Labels3
1. Monbu-kagaku-shō
2. 文部科学省
3. MEXT
Awards2
1. 12555252
2. 13650914

BibTeX

@article{Hasegawa_2002, title={Electroorganic synthesis under solvent-free conditions. Highly regioselective anodic monofluorination of cyclic ethers, lactones, and a cyclic carbonate}, volume={43}, ISSN={0040-4039}, url={http://dx.doi.org/10.1016/s0040-4039(02)00047-3}, DOI={10.1016/s0040-4039(02)00047-3}, number={8}, journal={Tetrahedron Letters}, publisher={Elsevier BV}, author={Hasegawa, Masaru and Ishii, Hideki and Fuchigami, Toshio}, year={2002}, month=feb, pages={1503–1505} }

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      "unstructured": "2-Fluoro-1,4-dioxane (4): colorless oil; 1H NMR (270 MHz, CDCl3) \u03b4 5.39 (d, J=52 Hz, 1H), 4.24 (m, 1H), 3.90\u20133.71 (m, 5H); 13C NMR (67.8 MHz, CDCl3) \u03b4 103.073 (d, J=221 Hz), 67.292 (d, J=25.7 Hz), 65.650, 60.671; 19F NMR (254 MHz, CDCl3) \u03b4 \u221261.1 (ddd, J=52, 35, 5.3 Hz); MS (m/z) 106 (M+), 87 (M+\u2212F), 86, 73; HRMS m/z calcd for C4H7FO2: 106.0430. Found: 106.0483."
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      "key": "10.1016/S0040-4039(02)00047-3_BIB10",
      "unstructured": "A typical procedure for the anodic fluorination is as follows. Anodic fluorination of 1 (4.90 g, 68.0 mmol) was carried out at platinum electrodes (2\u00d72 cm2) in 2.0 M Et4NF\u00b74HF (1.5 equiv. of F\u2212 to 1, a total volume of 1 and Et4NF\u00b74HF was 10 ml) in a cylindrical undivided cell under a nitrogen atmosphere at room temperature. Constant current (150 mA/cm2) was applied. After 2 F/mol of charge was passed, the corresponding fluorinated compound 2 (3.43 g, 38.1 mmol) was isolated by simple distillation of the electrolytic solution (bp 73\u00b0C)."
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      "key": "10.1016/S0040-4039(02)00047-3_BIB11",
      "unstructured": "2-Fluorotetrahydrofuran (2): colorless oil; 1H NMR (270 MHz, CDCl3) \u03b4 5.88 (d, J=67 Hz, 1H), 4.26\u20134.14 (m, 1H), 4.02\u20133.91 (m, 1H), 2.35\u20131.65 (m, 4H); 13C NMR (67.8 MHz, CDCl3) \u03b4 112.6769 (d, J=216 Hz), 69.414, 46.122, 33.172 (d, J=25.7 Hz), 21.719; 19F NMR (254 MHz, CDCl3) \u03b4 \u221234.8 (m); MS (m/z) 71 (M+\u2212F), 69, 43; HRMS m/z calcd for C4H7O (M+\u2212F): 71.0497. Found: 71.0487."
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