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DOI: https://doi.org/10.6023/cjoc202601037

研究论文

有机染料催化苄基C-H键的有氧光氧化

  • 李文静 ,
  • 刘春叶 ,
  • 梁玲玲 ,
  • 苗延青 ,
  • 尤静 ,
  • 沈思语
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  • 西安医学院药学院 西安 710021

收稿日期: 2026-03-20

  修回日期: 2026-04-08

  网络出版日期: 2026-06-04

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The Photochemical C-H Oxidation of Alkylarenes to Aldehydes and Ketones by an Organic Photocatalyst

  • Li Wenjing ,
  • Liu Chunye ,
  • Liang Lingling ,
  • Miao Yanqing ,
  • You Jing ,
  • Shen Siyu
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  • School of pharmacy, Xi'an Medical University, Xi'an, 710021

Received date: 2026-03-20

  Revised date: 2026-04-08

  Online published: 2026-06-04

Supported by

Foundation of Shaanxi Province Science and Technology Department of China (Nos. 2025JC-YBQN-136, 2025JC-YBMS-178), the Shaanxi Provincial Department of Education (No. 24JK0646) and Xi'an Medical University (Nos. 2023BS30).

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摘要

在光催化剂曙红Y的介导下,本文利用光氧化策略实现了苄基C(sp3)-H键的高选择性氧化,可将甲苯等烷基芳烃高效转化为相应的醛和酮,同时有效抑制过度氧化生成羧酸的副反应。该方法具备成本低廉、官能团兼容性优异、操作简便及合成实用性突出等显著优势。此外,克级规模实验进一步证实了其在酮类化合物制备中的应用潜力,且在最优反应条件下,以高产率合成乙酰乙酸乙酯和hCECE抑制剂。值得注意的是,本研究对反应机理及曙红Y的光物理特性展开了系统性探究。

关键词： 光催化; 曙红Y; 苄基C(sp3)-H; 醛和酮

本文引用格式

李文静 , 刘春叶 , 梁玲玲 , 苗延青 , 尤静 , 沈思语 . 有机染料催化苄基C-H键的有氧光氧化[J]. 有机化学, 0 : 0 . DOI: 10.6023/cjoc202601037

Abstract

Photooxygenation of benzylic C(sp3)-H by oxygen occurs efficiently under photoirradiation of Eosin Y to yield aldehydes and ketones, which is able to activate alkylarenes such as toluene and can overcome the overoxidation into carboxylic acids. This approach features cheap photocatalyst, broad substrate scope, easy scale up and further transformation. In addition, the photophysical characteristics of the Eosin Y and the reaction mechanism were also discussed.

Key words： photochemical; Eosin Y; benzylic C(sp3)-H; aldehydes and ketones

参考文献

[1] a) Franz, G.; Sheldon, R. A. Ullmann's Encyclopedia of Industrial Chemistry, 5th ed.; VCH: Weinheim, Germany, 1991. b) Sheldon, R. A.; Kochi, J. K. Metal Catalyzed Oxidation of Organic Compounds; Academic Press: New York, 1981; Chapter 10.
[2] a) Kahn B. E.; Rieke, R. D. Chem. Rev.1988, 88, 733. b) Jørgensen, K. A. Angew. Chem. Int. Ed. 2000, 39, 3558. c) Ravindar, L.; Lekkala, R.; Rakesh, K. P.; Asiri, A. M.; Marwanib, H. M.; Qin, H.-L. Org. Chem. Front. 2018, 5, 1381.
[3] a) Pokutsa A.; Tkach S.; Zaborovsky A.; Bloniarz P.; Paczeŝniak T.; Muzart J. ACS Omega.2020, 5, 7613-7626. b) Khursan, S. L.; Mikhailov, D. A.; Yanborisov, V. M.; Borisov, D. I. React. Kinet. Catal. Lett. 1997, 61, 91-95. c) Gao, J.; Tong, X. L.; Li, X. Q.; Miao, H.; Xu, J. J. Chem. Technol. Biotechnol. 2007, 82, 620-625. d) Li, X. Q.; Xu, J.; Wang, F.; Gao, J.; Zhou, L. P.; Yang, G. Y. Catal. Lett. 2006, 108, 137-140.
[4] a) Wang Y.; Chen X.; Jin H.; Wang Y. Chem.-Eur. J.2019, 25, 14273. b) Thirunavukkarasu, V. S.; Kozhushkov, S. I.; Ackermann, L. Chem. Commun. 2014, 50, 29.
[5] a) Zhang J.; Du J.; Zhang C.; Liu K.; Yu F.; Yuan Y.; Duan B.; Liu R. Org. Lett.2022, 24, 1152. b) Jaworski, J. N.; McCann, S. D.; Guzei, I. A.; Stahl, S. S. Angew. Chem. Int. Ed. 2017, 56, 3605. c) Choy, P. Y.; Kwong, F. Y. Org. Lett. 2013, 15, 270. d) Desai, Lopa V.; Hull, Kami L.; Sanford, Melanie S. J. Am. Chem. Soc. 2004, 126, 9542-9543.
[6] a) Wang J.; Zhang C.; Ye X.-Q.; Du W.; Zeng S.; Xua J.-H.; Yin H. RSC Adv.2021, 11, 3003. b) Nanjo, T.; De Lucca, E. C.; White, M. C. Remote, J. Am. Chem. Soc. 2017, 139, 14586. c) Chandra, B.; Singh, K. K.; Gupta, S. S. Chem. Sci. 2017, 8, 7545. d) Lindhorst, A. C.; Haslinger, S.; Kühn, F. E. Chem. Commun. 2015, 51, 17193-17212.
[7] a) Sauermann N.; Meyer T. H.; Tian C.; Ackermann, L. J. Am. Chem. Soc.2017, 139, 18452-18455. b) Hruszkewycz, D. P.; Miles, K. C.; Thiel, O. R.; Stahl, S. S. Chem. Sci. 2017, 8, 1282.
[8] a) Fukuzumi S.; Lee Y.-M.; Nam W. ChemSusChem.2019, 12, 3931. b) Burg, F.; Gicquel, M.; Breitenlechner, S.; Pöthig, A.; Bach, T. Angew. Chem. Int. Ed. 2018, 57, 2953. c) Olivo, G.; Farinelli, G.; Barbieri, A.; Lanzalunga, O.; Stefano, S. D.; Costas, M. Angew. Chem. Int. Ed. 2017, 56, 16347.
[9] Akhter Z.; Sharma S.; Anand R.; Samad M.; Verma, P; K; Singh, P. P. Org. Biomol. Chem.2025, 23, 5224-5233.
[10] a) Zeng Y.-Y.; Jiang J.; Wen Y.-C.; Zhuang C.-L.; Ou L.-J.; Yang Z.; Zhu H.-T.; Wang Z.-L.; He, W.-M. Chin. Chem. Lett.2026, 37, 111776. b) Zheng, K.; Chen, C.; Xu, H.; Mao, J.; Shen, C. J. Org. Chem. 2025, 90, 15567-15577. c) Shen, J.; Shen, C.; Zhang, P. Chin. J. Org. Chem. 2025, 45, 677. d) Duan, C.; Shen, S.; Zhao, Y.; Liu, Y.; Li, X.; Zhang, L.; Li, W. Chin. J. Org. Chem. 2025, 45, 1352. e) Lu, Y.; Zhao, J.; Sun, H.; Li, J.; Yu, Z.; Ma, C.; Zhu, H.; Meng, Q. J. Org. Chem. 2024, 89, 3868-3874. f) Tang, Y.; He, Y.; Yang, B.; Duan, J.; Du, C.; Jiang, J.; Li, J,; Pan, R.; Chen, Y.; Liu, X. Chin. J. Org. Chem. 2024, 44, 2286. g) Bo, C.; Bu, Q.; Liu, J.; Dai, B.; Liu, N. ACS Sustainable Chem. Eng. 2022, 10, 1822. h) Zhang, X.; Rakesh, K. P.; Ravindar, L.; Qin, H.-L. Green Chem. 2018, 20, 4790-4833.
[11] Wang Y.-H.; Yang Q.; Walsh P. J.; Schelter, E. J. Org. Chem. Front.2022, 9, 2612-2620.
[12] Hwang K. C.; Sagadevan A.; Kundu P. Green Chem.2019, 21, 6082-6088.
[13] Ma S.; Ma J-M.; Cui J.-W.; Rao C.-H.; Jia M.-Z.; Zhang J. Green Chem.2022, 24, 2492-2498.
[14] Wu J.; Chen J.; Wang Lei.; Zhu H.; Liu R.; Song G.; Feng C.; Li Y. Green Chem.2023, 25, 940-945.
[15] a) Ohkubo K.; Morikawa K.; Iwata R.; Souma K.; Suzuki N.; Fukuzumi S. Chem. Commun.2010, 46, 601-603. b) Ohkubo, K.; Suga, K.; Morikawa, K.; Fukuzumi, S. J. Am. Chem. Soc. 2003, 125, 12850-12859. c) Ohkubo, K.; Fukuzumi, S. Org. Lett. 2000, 2, 3647.
[16] a) Lechner R.; Kümmel S.; König B. Photobiol. Sci.2010, 9, 1367-1377. b) Mühldorf, B.; Wolf, R. Angew. Chem. Int. Ed. 2016, 55, 427. c) Mühldorf, B. and Wolf, R. Chem. Commun. 2015, 51, 8425-8429.
[17] Pandey G.; Pal S.; Laha, R. Angew. Chem. Int. Ed.2013, 52, 5146.
[18] Uygur M.; Kuhlmann J. H.; Pérez-Aguilar M. C.; Piekarski D. G.; Mancheño, O. G. Green Chem.2021, 23, 3392-3399.
[19] a) Li J.; Yu Z.; Zhao J.; Ma C.; Duan L.; Liu Z.; Sun H.; Zhao G.; Liu Q.; Meng, Q. J. Org. Chem.2025, 90, 1245-1255. b) Xu, Z.; Li, Y.; Mo, G.; Zheng, Y.; Zeng, S.; Sun, P.; Ruan, Z. Org. Lett. 2020, 22, 4016-4020.
[20] a) Han L.; Zhou H.; Hou J.; Shi X.; Li, Q. Org. Biomol. Chem. 2025, 23,3741-3799. b) Mondal, S.; Pandeosin, Y. A. M.; Gnanaprakasam, B.J. Org. Chem. 2024, 89, 3769-3780. c) Rajat and Jain, N. J. Org. Chem. 2023, 88, 8600-8608. d) Romero, N. A.; Nicewicz, D. A. Chem. Rev. 2016, 116, 10075-10166.
[21] a) Cheng F.; Fan L.; Lv Q.; Chen X.; Yu, Bing. Green Chem. 2023, 25,7971. b) Jia, M.-Z.; Cui, J.-W.; Rao, C.-H.; Chen, Y.-R.; Yao, X.-R.; Zhang. J.ACS Sustainable Chem. Eng. 2022, 10, 9591-9599. c) Nikitas, N. F.; Tzaras, D. I.; Triandafillidi I.; Kokotos, C. G. Green Chem. 2020, 22, 471-477.
[22] a) Singla D.; Luxami V.; Paul, K. Org. Chem. Front.2023, 10, 237-266. b) Bo, C.; Bu, Q.; Liu, J.; Dai, B.; Liu, N. ACS Sustainable Chem. Eng. 2022, 10, 1822-1828. c) Li, W.; Li, S.; Luo, L.; Ge, Y.; Xu, J.; Zheng, X.; Yuan, M.; Li, R.; Chen, H.; Fu, H. Green Chem. 2021, 23, 3649-3655. d) Chand, S.; Pandey, A. K.; Singh, R.; Kumar, S.; Singh, K. N. Chem. Asian J. 2019, 14, 4712-4716. e) Yang, T. L.; Lu, M. J.; Lin, Z. W.; Huang, M. Q.; Cai, S. Y. Org. Biomol. Chem. 2019, 17, 449-453. f) Ren, L.; Yang, M.-M.; Tung, C.-H.; Wu, L.-Z. Cong, H. ACS Catal. 2017, 7, 8134-8138. g) Liang, Z.; Xu, S.; Tian, W.; Zhang, R. Beilstein J. Org. Chem. 2015, 11, 425-430. h) Hari, D. P.; König, B. Org. Lett. 2011, 13, 3852-3855.
[23] a) Hari P.; König B. Chem. Commun.2014, 50, 6688-6699. b) Neumann, M.; Fldner, S.; Konig, B.; Zeitler, K. Angew. Chem. Int. Ed. 2011, 50, 951-954.
[24] a) Li W.; Liu C.; Liang L.; Zhang J.; Miao, Y. Org. Chem. Front. 2024, 11,5429-5436. b) Huang, W.; Ma, B. C.; Lu, H.; Li, R.; Wang, L.; Landfester K.; Zhang, K. A. I.ACS Catal. 2017, 7, 5438-5442. c) Li, R.; Wang, Z. J.; Wang, L.; Ma, B. C.; Ghasimi, S.; Lu, H.; Landfester, K.; Zhang, K. A. I. ACS Catal. 2016, 6, 1113-1121. d) Ghosh, S.; Kouame,Ń. A.; Ramos, L.; Remita, S.; Dazzi, A.; Deniset-Besseau, A.; Beaunier, P.; Goubard, F.; Aubert, P.-H.; Remita, H. Nat. Mater. 2015, 14, 505-511.
[25] Phulkar S.; Rao B. S. M.; Schuchmann H.-P.; Sonntag, C. V. Zeitschrift für Naturforschung B.1990, 45, 1425-1432.
[26] a) Chen, H.; Mi, M.; Wang, C.; Li, A.; Qi Y and Liu, Y.Org. Biomol. Chem. 2025, 23, 3137-3142. b) Dilauro, G.; Azzollini, C. S.; Vitale, P.; Salomone, A.; Perna, F. M.; Capriati, V. Angew. Chem. Int. Ed. 2021, 60, 10632-10636. c) Fan, Q.; Liu, D.; Xie, Z.; Le, Z.; Zhu, H.; Song, X. J. Org. Chem. 2023, 88, 14559-14570. d) Asmaul Hoque, Md; Schweinzer, C.; Martinez, J. J.; Tewes, F.; Sacchetti, V.; Grützmacher, H.; Stahl, S. S. Angew. Chem. Int. Ed. 2025, 64, e202424778. e) Shigemura, S.; Kurahashi, T. Synlett. 2024, 36, 894-898. f) Murata, T.; Tsutsui, H.; Shiina I. J. Org. Chem. 2024, 89, 15414-15435. g) Zimmerman, S. S.; Alpa, K.; Garnier-Amblard, E. C.; Mullasseril P.; Kurtkaya, N. L.; Gyoneva, S.; Hansen, K. B.; Traynelis, S. F.; Liotta, D. C. J. Med. Chem. 2014, 57, 2334-2356. h) Gu, J.; Wan, Y.; Ma, H.; Zhu, H.; Bu, H.; Zhou, Y.; Zhang, W.; Wu, Z.; Li, Y. Tetrahedron. 2021, 93, 132298. i) Tripathi, S.; Chakravarty, M. Chemistry-A European Journal. 2025, 31, e202403300. j) Zhong, J.; Zhou, W.; Yan, X.; Xia, Y.; Xiang, H.; Zhou, X. Org. Lett. 2022, 24, 1372-1377. k) Ai, J.-J.; Liu, B.-B.; Li, J.; Wang, F.; Huang, C.-M.; Rao, W.; Wang, S.-Y. Org. Lett. 2021, 23, 4705-4709. l) Sharma, P.; Rohilla, S.; Jain, N. J. Org. Chem. 2017, 82, 1105-1113. m) Zhang, J.; Du, J.; Zhang, C.; Liu, K.; Yu, F.; Yuan, Y.; Duan, B.; Liu, R. Org. Lett. 2022, 24, 1152-1157. n) Kuang, Y.; Wang, Y. Eur. J. Org. Chem. 2014, 6, 1163-1166. o) Fan, J.; Peng, Y.; Xu, W.; Wang, A.; Xu, J.; Yu, H.; Lin, X.; Wu, Q. Org. Lett. 2020, 22, 5446-5450. p) Ruan, L.; Shi, M.; Li, N.; Ding, X.; Yang, F.; Tang, J. Org. Lett. 2014, 16, 733-735.
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