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

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

Cite this article

Li Wenjing, Liu Chunye, Liang Lingling, Miao Yanqing, You Jing, Shen Siyu. The Photochemical C-H Oxidation of Alkylarenes to Aldehydes and Ketones by an Organic Photocatalyst[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202601037.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[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.

有机染料催化苄基C-H键的有氧光氧化