可见光驱动下蒽醌催化苄基C—H键在水中的氧化反应

doi:10.6023/cjoc202406032

摘要/Abstract

发展了一种高效的可见光催化烷基芳烃氧化成酮的反应, 以蒽醌作有机小分子光催化剂, 氧气为氧化剂, 水为绿色溶剂. 该方法主要特征在于使用了可见光、氧分子和水, 其成本低, 含量丰富, 生态友好性强. 此外, 该方法具有广泛的底物范围和良好的官能团耐受性, 并且能扩大到克级. 通过一系列的控制实验, 研究了超氧自由基对反应的影响, 提出了合理的催化循环机理. 机理研究表明, 蒽醌吸收可见光作为光敏剂促进氧气通过单电子转移生成活性单线态氧, 从而氧化烷基芳烃成酮.

关键词: 可见光催化, 烷基芳烃, 酮, 蒽醌, 水

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 can also easily be scaled-up to gram scale. A series of control experiments was conducted to study the influence of superoxide radicals on the reaction, and a reasonable catalytic cycle mechanism was proposed. The mechanism studies revealed that AQ absorbed the light and served as a photosensitizer to promote the transformation of O₂ to the highly reactive $\text{O}_{2}^{\centerdot }$ via single electron transfer (SET) process, which then oxidized alkylarenes to ketones.

Key words: visible-light photocatalysis, alkylarene, ketone, anthraquinone, water

引用此文

段琛, 沈思语, 赵钰琦, 刘跃, 李薪宇, 张礼智, 李文静. 可见光驱动下蒽醌催化苄基C—H键在水中的氧化反应[J]. 有机化学, 2025, 45(4): 1352-1359.

Chen Duan, Siyu Shen, Yuqi Zhao, Yue Liu, Xinyu Li, Lizhi Zhang, Wenjing Li. Visible-Light-Driven Oxidation of Benzylic C—H Bonds Enabled by Anthraquinone in Water[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1352-1359.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 9

图1. 含苄基酮的药物分子

Figure 1. Pharmaceutical compounds containing benzyl ketones

图式1. 可见光诱导苄基C—H键的氧化反应

Scheme 1. Visible-light-initiated oxidation of benzyl C—H bond

Entry	Light source	Solvents	Yield^b/%
1	Blue LED	CH₃CN	Trace
2	Blue LED	CH₃CN	NR
3	Blue LED	CH₃CN	NR
4	Blue LED	CH₃CN	21
5	Blue LED	CH₃CN	33
6	Blue LED	CH₃CN	45
7	Blue LED	DCE	63
8	Blue LED	MeOH	56
9	Blue LED	1,4-Dioxane	39
10	Blue LED	THF	18
11	Blue LED	DMSO	31
12	Blue LED	DMF	40
13	Blue LED	H₂O	59
14^c	Blue LED	H₂O	78
15	UV	H₂O	79

表1. 实验条件优化a

Table 1. Optimization of reaction conditions

表2. 苄基C—H键的氧化生成相应的芳香酮a,b

Table 2. Oxidation of benzyl C—H bond to form the aromatic ketones

图式2. 二苯甲酮2a的放大量合成

Scheme 2. Large-scale synthesis of benzophenone 2a

图式3. 控制实验

Scheme 3. Control experiments

图2. 开关灯实验

Figure 2. On/off experiment

图3. (a) AQ、1a (1.0×10－3 mol/L)以及(b) AQ＋1a、AQ (1.0×10－3 mol/L)的紫外可见吸收光谱

Figure 3. Absorption spectra of (a) AQ, 1a (1.0×10－3 mol/L) and (b) AQ＋1a, AQ (1.0×10－3 mol/L)

图式4. 推测的催化循环机理图

Scheme 4. Proposed mechanism

参考文献 21

[1]	(a) Xie, W.; Wu, Y.; Zhang, J.; Mei, Q.; Zhang, Y.; Zhu, N.; Liu, R.; Zhang, H. Eur. J. Med. Chem. 2018, 145, 35.
	(b) Erve, J. C. L.; Gauby, S.; Maynard, J. W.; Svensson, M. A.; Tonn, G.; Quinn, K. P. Chem. Res. Toxicol. 2013, 26, 926.
[2]	European Food Safety Authority EFSA J. 2013, 11, 3147.
[3]	Wang, Y.; Chen, X.; Jin, H.; Wang, Y. Chem.-Eur. J. 2019, 25, 14273. doi: 10.1002/chem.201902739 pmid: 31361049
[4]	(a) Zhang, J.; Du, J.; Zhang, C.; Liu, K.; Yu, F.; Yuan, Y.; Duan, B.; Liu, R. Org. Lett. 2022, 24, 1152. pmid: 15291549
	(b) Jaworski, J. N.; McCann, S. D.; Guzei, I. A.; Stahl, S. S. Angew. Chem., Int. Ed. 2017, 56, 3605. pmid: 15291549
	(c) Desai, L. V.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 9542. pmid: 15291549
[5]	(a) Hruszkewycz, D. P.; Miles, K. C.; Thiel, O. R.; Stahl, S. S. Chem. Sci. 2017, 8, 1282. doi: 10.1039/c6sc03831j pmid: 29149561
	(b) Sauermann, N.; Meyer, T.; Tian, C.; Ackermann, L. J. Am. Chem. Soc. 2017, 139, 18452. doi: 10.1021/jacs.7b11025 pmid: 29149561
[6]	(a) Wang, J.; Zhang, C.; Ye, X.-Q.; Du, W.; Zeng, S.; Xua, J.-H.; Yin, H. RSC Adv. 2021, 11, 3003. pmid: 24020940
	(b) Nanjo, T.; De Lucca, E. C.; White, M. C. J. Am. Chem. Soc. 2017, 139, 14586. pmid: 24020940
	(c) Chandra, B.; Singh, K. K.; Gupta, S. S. Chem. Sci. 2017, 8, 7545. doi: 10.1039/c7sc02780j pmid: 24020940
	(d) Ammann, S. E.; Liu, W.; White, M. C. Angew. Chem., Int. Ed. 2016, 55, 9571. pmid: 24020940
	(e) Gormisky, P. E.; White, M. C. J. Am. Chem. Soc. 2013, 135, 14052. doi: 10.1021/ja407388y pmid: 24020940
	(f) Chen, M. S.; White, M. C. Science 2007, 318, 783. pmid: 24020940
[7]	Olivo, G.; Farinelli, G.; Barbieri, A.; Lanzalunga, O.; Stefano, S. D.; Costas, M. Angew. Chem., Int. Ed. 2017, 56, 16347.
[8]	Simmons, E. M.; Hartwig, J. F. Nature 2012, 482, 70.
[9]	Liu, K.-J.; Duan, Z.-H.; Zeng, X.-L.; Sun, M.; Tang, Z.; Jiang, S.; Cao, Z.; He, W.-M. ACS Sustainable Chem. Eng. 2019, 7, 10293.
[10]	Bo, C.; Bu, Q.; Liu, J.; Dai, B.; Liu, N. ACS Sustainable Chem. Eng. 2022, 10, 1822.
[11]	Wu, J.; Chen, J.; Wang, L.; Zhu, H.; Liu, R.; Song, G.; Feng, C.; Li, Y. Green Chem. 2023, 25, 940.
[12]	Niu, K.; Shi, X.; Ding, L.; Liu, Y.; Song, H.; Wang, Q. ChemSusChem 2022, 15, e202102326.
[13]	(a) Tang, C.; Qiu, X.; Cheng, Z.; Jiao, N. Chem. Soc. Rev. 2021, 50, 8067.
	(b) Cheng, X.; Hu, X.; Lu, Z. Chin. J. Org. Chem. 2017, 37, 251 (in Chinese).
	(程骁恺, 胡新根, 陆展, 有机化学, 2017, 37, 251.) doi: 10.6023/cjoc201609022
	(c) Bian, C.; Singh, A. K.; Niu, L.; Yi. ; Lei, A. Asian J. Org. Chem. 2017, 6, 386.
[14]	(a) Li, Z.; Wan, Z.; Wang, W.; Chen, L.; Ji, P. ACS Catal. 2024, 14, 8786.
	(b) Zhu, C.-M.; Liang, R.-B.; Xiao, Y.; Zhou, W.; Tong, Q.-X.; Zhong, J.-J. Green Chem. 2023, 25, 960.
	(c) Xu, N.; Peng, X.; Luo, C.; Huang, L.; Wang, C.; Chen, Z.; Li, J. Adv. Synth. Catal. 2023, 365, 142.
	(d) Li, S.; Tian, D.; Zhao, X.; Yin, Y.; Lee, R.; Jiang, Z. Org. Chem. Front. 2022, 9, 6229.
	(e) Uygur, M.; Kuhlmann, J. H.; Pérez-Aguilar, M. C.; Piekarski, D. G.; Mancheño, O. G. Green Chem. 2021, 23, 3392.
	(f) Li, S.; Zhu, B.; Lee, R.; Qiao, B.; Jiang, Z. Org. Chem. Front. 2018, 5, 380.
	(g) Liu, X.; Lin, L.; Ye, X.; Tan, C.-H.; Jiang, Z. Asian J. Org. Chem. 2017, 6, 422.
[15]	Zhang, W.; Gacs, J.; Arends, I. W. C. E.; Hollmann, F. ChemCatChem 2017, 9, 3821.
[16]	Zhu, X.; Liu, Y.; Liu, C.; Yang, H.; Fu, H. Green Chem. 2020, 22, 4357.
[17]	Ma, S.; Ma, J.-M.; Cui, J.-W.; Rao, C.-H.; Jia, M.-Z.; Zhang, J. Green Chem. 2022, 24, 2492.
[18]	(a) Zhao, J.; Sun, H.; Lu, Yue.; Li, J.; Yu, Z.; Zhu, H.; Ma, C.; Meng, Q.; Peng, X. Green Chem. 2022, 24, 8503.
	(b) Zhou, C.; Lei, T.; Wei, X.-Z.; Ye, C.; Liu, Z.; Chen, B.; Tung, C.-H.; Wu, L.-Z. J. Am. Chem. Soc. 2020, 142, 16805.
[19]	(a) Liang, Z.; Yu, Y.; Zhang, L.; Xue, G.; Liu, M.; Zhang, Y.; Huang, M.; Cai, L.; Cai, S. Org. Lett. 2024, 26, 298.
	(b) Saini, S.; Shafiur, R. K.; Gour, N. K.; Deka, R. C.; Jain, S. L. Green Chem. 2022, 24, 3644.
	(c) Cervantes-González, J.; Vosburg, D. A.; Mora-Rodriguez, S.; Vázquez, M. A.; Zepeda, L. G.; Gómez, C. V.; Lagunas-Rivera, S. ChemCatChem 2020, 12, 3811.
[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.
	(b) Li, J.; Bao, W.; Tang, Z.; Guo, B.; Zhang, S.; Liu, H.; Huang, S.; Zhang, Y.; Rao, Y. Green Chem. 2019, 21, 6073.
	(c) Yi, H.; Bian, C.; Hu, X.; Niu, L.; Lei, A. Chem. Commun. 2015, 51, 14046.
[21]	(a) Ni, S.; Zhang, W.; Mei, H.; Han, J.; Pan, Y. Org. Lett. 2017, 19, 2536.
	(b) Xie, P.; Xue, C.; Du, D.; Shi, S. Org. Biomol. Chem. 2021, 19, 6781.
	(c) Yu, T.; Guo, M.; Wen, S.; Zhao, R.; Wang, J.; Sun, Y.; Liu, Q.; Zhou, H. RSC Adv. 2021, 11, 13848.