Photochemical Oxidation of Benzylic C-H bonds Enabled by Anthraquinone in Water

doi:10.6023/cjoc202406032

Abstract

An efficient photochemical protocol for the oxidation of alkylarenes to ketones was developed using anthraquinone (AQ) as a organic small molecule photocatalysts, O₂ as an oxidant and water as green solvent. The main feature of this method is that visible light, molecular oxygen and water are low-cost, abundance and eco-friendliness in green chemistry. Moreover, the system shows a broad substrate scope and good functional-group tolerance, which also can easily be scaled-up to gram scale. Some control experiments were also conducted to support a possible reaction pathway and the mechanism studies revealed that AQ absorbed the light and served as a photosensitizer to promote the transformation of O₂ to the highly reactive O₂^•- via single electron transfer (SET) process, which then oxidized alkylarenes to ketones.

Key words: photochemical, alkylarenes, ketones, anthraquinone, water

Cite this article

Chen Duan, Siyu Shen, Yuqi Zhao, Yue Liu, Xinyu Li, Lizhi Zhang, Wenjing Li. Photochemical Oxidation of Benzylic C-H bonds Enabled by Anthraquinone in Water[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202406032.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Xie, W.; Wu, Y.; Zhang, J.; Mei, Q.; Zhang, Y.; Zhu, N.; Liu, R.; Zhang, H. Design, Eur. J. Med. Chem. 2018, 145, 35-40.(b) Erve, J. C. L.; Gauby, S.; Maynard, J. W.; Svensson, M. A.; Tonn, G.; Quinn, K. P. Chem. Res. Toxicol. 2013, 26, 926-936.
[2] European Food Safety Authority. Conclusion on the peer review of the pesticide risk assessment of the active substance pyriofenone. EFSA J.2013, 11, No. 3147.
[3] Wang, Y.; Chen, X.; Jin H. and Wang, Y. Chem. Eur. J. 2019, 25, 14273-14277.
[4] (a) Zhang, J.; Du, J.; Zhang, C.; Liu, K.; Yu, F.; Yuan, Y.; Duan, B. and Liu, R. Org. Lett. 2022, 24, 1152-1157.(b) Jaworski, J. N.; McCann, S. D.; Guzei, I. A.; Stahl, S. S. Angew. Chem., Int. Ed. 2017, 56, 3605-3610.(c) Desai, L. V.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 9542-9543.
[5] (a) Hruszkewycz, D. P.; Miles, K. C.; Thiel, O. R.; Stahl, S. S. Chem. Sci. 2017, 8, 1282-1287.(b) Sauermann, N.; Meyer, T.; Tian, C.; Ackermann, L. J. Am. Chem. Soc. 2017, 139, 18452-18455.
[6] (a) Wang, J.; Zhang, C.; Ye, X.-Q.; Du, W.; Zeng, S.; Xua, J.-H. and Yin, H. RSC Adv. 2021, 11, 3003-011.(b) Nanjo, T.; De Lucca, E. C.; White, M. C. J. Am. Chem. Soc. 2017, 139, 14586-14591.(c) Chandra, B.; Singh, K. K.; Gupta, S. S. Chem. Sci. 2017, 8, 7545-7551. (d) Ammann, S. E.; Liu, W.; White, M. C. Angew. Chem., Int. Ed. 2016, 55, 9571-9575. (e) Gormisky, P. E.; White, M. C. J. Am. Chem. Soc. 2013, 135, 14052-14055. (f) Chen, M. S.; White, M. C. Science. 2007, 318, 783-787.
[7] Olivo, G.; Farinelli, G.; Barbieri, A.; Lanzalunga, O.; Stefano, S. D.; Costas, M. Angew. Chem., Int. Ed. 2017, 56, 16347-16351.
[8] Simmons, E. M.; Hartwig, J. F. Nature. 2012, 482, 70-73.
[9] Liu, K.-J.; Duan, Z.-H.; Zeng, X.-L.; Sun, M.; Tang, Z.; Jiang, S.; Cao, Z. and He, W.-M. ACS Sustainable Chem. Eng. 2019, 7, 10293-10298.
[10] Bo, C.; Bu, Q.; Liu, J.; Dai B. and Liu, N. ACS Sustainable Chem. Eng. 2022, 10, 1822-1828.
[11] Wu, J.; Chen, J.; Wang, L.; Zhu, H.; Liu, R.; Song, G.; Feng C. and Li, Y. Green Chem. 2023, 25, 940-945.
[12] Niu K.; Shi X.; Ding L.; Liu Y.; Song H. and Wang Q. ChemSusChem.2022, 15, e202102326 (1 of 5).
[13] (a) Tang, C.; Qiu, X.; Cheng Z. and Jiao, N. Chem. Soc. Rev., 2021, 50, 8067-8101(b) Cheng X.; Hu X.; Lu Z. Chin. J. Org. Chem., 2017, 37, 251-266;(c) Bian, C.; Singh, A. K.; Niu, L.; Yi, Hong.; Lei, A. Asian J. Org. Chem., 2017, 6, 386-396.
[14] (a) Li, Z.; Wan, Z.; Wang, W.; Chen, L. and Ji, P. ACS Catal., 2024, 14, 8786-8793(b) Zhu, C.-M.; Liang, R.-B.; Xiao, Y.; Zhou, W.; Tong Q.-X. and Zhong, J.-J. Green Chem., 2023, 25, 960-965;(c) Xu, N.; Peng, X.; Luo, C.; Huang, L.; Wang, C.; Chen, Z.; Li, J. Adv. Synth. Catal., 2023, 365, 142-147; (d) Li, S.; Tian, D.; Zhao, X.; Yin, Y.; Lee, R. and Jiang, Z. Org. Chem. Front., 2022, 9, 6229-6239; (e) Uygur, M.; Kuhlmann, J. H.; Pérez-Aguilar, M. C.; Piekarski, D. G. and Mancheño, O. G. Green Chem., 2021, 23, 3392-3399; (f) Li, S.; Zhu, B.; Lee, R.; Qiao B. and Jiang, Z. Org. Chem. Front., 2018, 5, 380-385; (g) Liu, X.; Lin, L.; Ye, X.; Tan, C.-H.; Jiang, Z. Asian J. Org. Chem., 2017, 6, 422-425.
[15] Zhang, W.; Gacs, J.; Arends, I. W.C.E. and Hollmann, F. ChemCatChem. 2017, 9, 3821-3826.
[16] Zhu, X.; Liu, Y.; Liu, C.; Yang H. and Fu, H. Green Chem. 2020, 22, 4357-4363.
[17] Ma, S.; Ma, J.-M.; Cui, J.-W.; Rao, C.-H.; Jia M.-Z. and Zhang, J. Green Chem. 2022, 24, 2492-2498.
[18] (a) Zhao, J.; Sun, H.; Lu, Yue.; Li, J.; Yu, Z.; Zhu, H.; Ma, C.; Meng Q. and Peng, X. Green Chem. 2022, 24, 8503-8511.(b) Zhou, C.; Lei, T.; Wei, X.-Z.; Ye, C.; Liu, Z.; Chen B.; Tung, C.-H. and Wu, L.-Z. J. Am. Chem. Soc. 2020, 142, 16805-16813.
[19] (a) Liang, Z.; Yu, Y.; Zhang, L.; Xue, G.; Liu, M.; Zhang, Y.; Huang, M.; Cai L. and Cai, S. Org. Lett. 2024, 26, 298-303.(b) Saini, S.; Shafiur, R. K.; Gour, N. K.; Deka R. C. and Jain, S. L. Green Chem. 2022, 24, 3644-3650.(c) Cervantes-González, J.; Vosburg, D. A.; Mora-Rodriguez, S.; Vázquez, M. A.; Zepeda, L. G.; Gómez, C. V. and Lagunas-Rivera S. ChemCatChem. 2020, 12, 3811-3827.
[20] (a) 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.(b) Zhu, X.; Liu, Y.; Liu, C.; Yang, H.; Fu, H. Green Chem. 2020, 22, 4357-4363.(c) Li, J.; Bao, W.; Tang, Z.; Guo, B.; Zhang, S.; Liu, H.; Huang, S.; Zhang, Y.; Rao, Y. Green Chem. 2019, 21, 6073-6081. (d) Yi, H.; Bian, C.; Hu, X.; Niu, L.; Lei, A. Chem. Commun. 2015, 51, 14046-14049.
[21] (a) Ni, S.; Zhang, W.; Mei, H.; Han, J. and Pan, Y. Org. Lett., 2017, 19, 2536-2539(b) Xie, P.; Xue, C.; Du, D. and Shi, S. Org. Biomol. Chem., 2021, 19, 6781-6785;(c) Yu, T.; Guo, M.; Wen, S.; Zhao, R.; Wang, J.; Sun, Y.; Liu, Q. and Zhou, H. RSC Adv., 2021, 11, 13848-13852; (d) Liu, K.-J.; Duan, Z.-H.; Zeng, X.-L.; Sun, M.; Tang, Z.; Jiang, S.; Cao, Z. and He, W.-M. ACS Sustainable Chem. Eng., 2019, 7, 10293-10298.

可见光驱动下蒽醌催化苄基C-H键在水中的氧化反应