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2026 26080283

DOI: https://doi.org/10.6023/A26080283

Cobalt Fluoride Complex Catalyzed Fluorination of Acyl- and Sulfonyl Chlorides

  • Bing-Bin Yang ,
  • Chen-Xu Gong ,
  • Ye-Rong Chen ,
  • Xing-lei He ,
  • Bin Zhao ,
  • Chun Yu ,
  • Ke-Yin Ye
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  • aFujian Key Laboratory of Flexible Electronics, Strait Institute of Flexible Electronics (SIFE, Future Technologies), Fujian Normal University, Fuzhou, 350117, China;
    bLaboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350108

Received date: 2026-08-12

  Online published: 2026-09-23

Supported by

National Natural Science Foundation of China (22171046).

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Abstract

Acyl fluorides are valuable intermediates in organic synthesis and have found broad applications in medicinal chemistry and functional materials. However, established synthetic methods often rely on unstable or hazardous fluorinating reagents, harsh reaction conditions, or expensive catalysts, thereby limiting their practical utility. Herein, we report an air-compatible fluorination of acyl chlorides and sulfonyl chlorides catalyzed by the cobalt fluoride complex [CoF3(terpy)]·MeOH·H2O (terpy = 2,2′:6′,2″-terpyridine), with inexpensive and readily available potassium fluoride (KF) serving as the terminal fluoride source. In a typical procedure, an oven-dried Schlenk tube equipped with a magnetic stir bar was charged with an acyl chloride or sulfonyl chloride (0.20 mmol), [CoF3(terpy)]·MeOH·H2O (0.010 mmol, 5.0 mol%), KF (0.40 mmol, 2.0 equiv.), and acetonitrile (2.0 mL). The mixture was stirred in air at 25 °C for 10 h. After completion of the reaction, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography. Under the optimized conditions, benzoyl chloride was converted to benzoyl fluoride in 99% yield. Moreover, the catalytic system exhibited good reactivity and functional-group tolerance toward electronically and structurally diverse acyl and sulfonyl chlorides. Notably, it enabled the preparation of functional products, including a coumarin-derived fragrance and the fluorescent inhibitor dansyl fluoride. A gram-scale reaction conducted on a 5.0 mmol scale afforded 1.21 g of the target sulfonyl fluoride in 96% yield, demonstrating the preparative utility of the method. Density functional theory calculations indicated that fluoride transfer from the axial Co-F bond is kinetically favored over transfer from the equatorial Co-F bond, with calculated activation free energies of 23.2 and 26.9 kcal·mol⁻¹, respectively. Mulliken charge analysis further suggested that the axial fluoride ligand has greater nucleophilic character. Collectively, these results support a plausible catalytic pathway involving fluoride transfer from the axial Co-F bond to the carbonyl carbon of the acyl chloride, followed by regeneration of the cobalt fluoride catalyst by KF. Overall, this protocol features mild reaction conditions, operational simplicity, broad substrate scope, and good functional-group tolerance, providing a practical and economical route to acyl fluorides and sulfonyl fluorides.

Key words： cobalt fluoride complex; acyl fluoride; sulfonyl fluoride; fluorination; fluorine-chlorine exchange

Cite this article

Bing-Bin Yang , Chen-Xu Gong , Ye-Rong Chen , Xing-lei He , Bin Zhao , Chun Yu , Ke-Yin Ye . Cobalt Fluoride Complex Catalyzed Fluorination of Acyl- and Sulfonyl Chlorides[J]. Acta Chimica Sinica, 2026 : 26080283 . DOI: 10.6023/A26080283

References

[1] (a) Ueda, T.; Konishi, H.; Manabe, K. Org. Lett. 2013, 15, 5370.
(b) Zhang, Y.; Rovis, T. J. Am. Chem. Soc. 2004, 126, 15964.
(c) Li, X.; Wu, L. Chin. J. Chem. 2024, 42, 3429.
(d) Zhao, J.; Gan, Q.-Y.; Yuan, Y.-F. Chin. J. Org. Chem. 2025, 45, 1206 (in Chinese).
(赵佳, 甘秋云, 袁耀锋, 有机化学, 2025, 45, 1206.)
[2] Pulikkottil F.; Burnett J. S.; Saiter J.; Goodall C. A. I.; Claringbold B.; Lam K. Org. Lett.2024, 26, 6103.
[3] Zhang C.; Chen J.; Wang K.; Wu, W.-K. Zhejiang Chem. Ind.2024, 55, 1 (in Chinese).
(张超, 陈建, 王焜, 吴文康, 浙江化工, 2024, 55, 1.)
[4] Qiu, K.-H. Zhejiang Chem. Ind. 2023, 54, 1 (in Chinese).
(邱堪辉, 浙江化工, 2023, 54, 1.)
[5] (a) Lee, I.; Shim, C. S.; Chung, S. Y.; Kim, H. Y.; Lee, H. W. J. Chem. Soc., Perkin Trans. 2. 1988, 1919.
(b) Clark, J. H.; Hyde, A. J.; Smith, D. K. J. Chem. Soc., Chem. Commun. 1986, 791.
(c) Tullock, C. W.; Coffman, D. D. J. Org. Chem. 1960, 25, 2016.
(d) Bhadury, P. S.; Pandey, M.; Jaiswal, D. K. J. Fluorine Chem. 1995, 73, 185.
(e) Olah, G. A.; Welch, J. T.; Vankar, Y. D.; Nojima, M.; Kerekes, I.; Olah, J. A. J. Org. Chem. 1979, 44, 3872.
(f) Blicke, F. F. J. Am. Chem. Soc. 1924, 46, 1515.
[6] (a) Chen, C.; Chien, C.-T.; Su, C.-H. J. Fluorine Chem. 2002, 115, 75.
(b) Ritter, S. K.; Hill, B. K.; Odian, M. A.; Dai, J.; Noftle, R. E.; Gard, G. L. J. Fluorine Chem. 1999, 93, 73.
(c) Yang, Z.; Chen, S.; Yang, F.; Zhang, C.; Dou, Y.; Zhou, Q.; Yan, Y.; Tang, L. Eur. J. Org. Chem. 2019, 2019, 5998.
(d) Munoz, S. B.; Dang, H.; Ispizua-Rodriguez, X.; Mathew, T.; Prakash, G. K. S. Org. Lett. 2019, 21, 1659.
(e) Hasek, W. R.; Smith, W. C.; Engelhardt, V. A. J. Am. Chem. Soc. 1960, 82, 543.
(f) Patrick, T. B.; Johri, K. K.; White, D. H.; Bertrand, W. S.; Mokhtar, R.; Kilbourn, M. R.; Welch, M. J. Can. J. Chem. 1986, 64, 138.
(g) Song, Z.-D.; Jiang, L.-Q.; Yi, W.-B. Acta Chim. Sinica 2018, 76, 967 (in Chinese).
(宋治东, 蒋绿齐, 易文斌, 化学学报, 2018, 76, 967.)
(h) Ran, L.-Y.; Zhang, C.-P. Chin. J. Org. Chem. 2022, 42, 2045 (in Chinese).
(冉龙玉, 张成潘, 有机化学, 2022, 42, 2045.)
(i) Liu, X.-J.; Xu, B.-P.; Su, W.-P. Chin. J. Org. Chem. 2022, 42, 2184 (in Chinese).
(刘晓洁, 徐必平, 苏伟平, 有机化学, 2022, 42, 2184.)
(j) Zhao, S.; Guo, Y.; Su, Z.; Wu, C.; Chen, W.; Chen, Q.-Y. Chin. J. Chem. 2021, 39, 1225.
[7] (a) Liang Y.; Zhao Z.; Taya A.; Shibata N. Org. Lett.2021, 23, 847.
(b) Stavber, S.; Planinsek, Z.; Zupan, M. J. Org. Chem. 1992, 57, 5334.
(c) Meanwell M.; Lehmann J.; Eichenberger M.; Martin R. E.; Britton R. Chem. Commun.2018, 54, 9985.
[8] Sakakura T.; Chaisupakitsin M.; Hayashi T.; Tanaka, M. J. Organomet. Chem.1987, 334, 205.
[9] (a) Guo, P.; Dong, S.; Zhang, X.-G.; Yang, B.-B.; Zhu, J.; Ye, K.-Y. Chin. Chem. Lett. 2025, 36, 110052.
(b) Yang, B.-B.; Guo, P.; He, X.; Ye, K.-Y. Org. Chem. Front. 2024, 11, 4125.
(c) Guo, P.; Li, Y.; Zhang, X.-G.; Han, J.-F.; Yu, Y.; Zhu, J.; Ye, K.-Y. Org. Lett. 2020, 22, 3601.
(d) Zhang, X.-G.; Guo, P.; Han, J.-F.; Ye, K.-Y. Chem. Commun. 2020, 56, 8512.
(e) Guo, P.; Han, J.-F.; Yuan, G.-C.; Chen, L.; Liao, J.-B.; Ye, K.-Y. Org. Lett. 2021, 23, 4067.
[10] (a) Lee G. M.; Clément R.; Baker, R. T. Catal. Sci. Technol.2017, 7, 4996.
(b) Leclerc M. C.; Bayne J. M.; Lee G. M.; Gorelsky S. I.; Vasiliu M.; Korobkov I.; Harrison D. J.; Dixon D. A.; Baker, R. T. J. Am. Chem. Soc.2015, 137, 16064.
[11] Li W. H.; Ye B. C.; Yang J.; Wang Y.; Yang C. J.; Pan Y. M.; Tang H. T.; Wang D.; Li, Y. Angew. Chem., Int. Ed.2022, 61, e202209749.
[12] (a) Han Z.; Cui Y.; Ding C.-R.; Yang J.; Zhang, G.-F. Chin. J. Org. Chem.2025, 45, 2245 (in Chinese).
(韩哲, 崔银, 丁成荣, 杨建, 张国富, 有机化学, 2025, 45, 2245.)
(b) Zhao, B.; Zeng, D.-B.; He, X.; Li, J.-H.; Lin, Y.; Ye, K.-Y. JACS Au 2025, 5, 2359., 9316.
[13] García-Abellán S.; Barrena-Espés D.; Munarriz J.; Passarelli V.; Iglesias M. Dalton Trans.2023, 52, 4585.
[14] Blower P. J.; Levason W.; Luthra S. K.; McRobbie G.; Monzittu F. M.; Mules T. O.; Reid G.; Subhan, M. N. Dalton Trans.2019, 48, 6767.
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