Visible-Light-Driven Oxidation of Benzylic C—H Bonds Enabled by Anthraquinone in Water

doi:10.6023/cjoc202406032

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (4): 1352-1359.DOI: 10.6023/cjoc202406032 Previous Articles Next Articles

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可见光驱动下蒽醌催化苄基C—H键在水中的氧化反应

段琛, 沈思语, 赵钰琦, 刘跃, 李薪宇, 张礼智, 李文静^*()

西安医学院药学院西安 710021

收稿日期:2024-08-13 修回日期:2024-09-16 发布日期:2024-10-10
基金资助:
西安医学院博士启动基金(2023BS30); 陕西省教育厅(24JK0646); 国家级大学生创新创业(202311840007)

Visible-Light-Driven Oxidation of Benzylic C—H Bonds Enabled by Anthraquinone in Water

Chen Duan, Siyu Shen, Yuqi Zhao, Yue Liu, Xinyu Li, Lizhi Zhang, Wenjing Li()

School of Pharmacy, Xi'an Medical University, Xi'an 710021

Received:2024-08-13 Revised:2024-09-16 Published:2024-10-10
Contact: * E-mail: liwenjing@xiyi.edu.cn
Supported by:
Xi'an Medical University(2023BS30); Shaanxi Provincial Department of Education(24JK0646); National College Students’ Innovation and Entrepreneurship Training Program(202311840007)

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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 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

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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.

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Fig. & Tab. 9

Figure 1. Pharmaceutical compounds containing benzyl ketones

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

Table 1. Optimization of reaction conditions

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

Scheme 2. Large-scale synthesis of benzophenone 2a

Scheme 3. Control experiments

Figure 2. On/off experiment

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)

Scheme 4. Proposed mechanism

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可见光驱动下蒽醌催化苄基C—H键在水中的氧化反应

Visible-Light-Driven Oxidation of Benzylic C—H Bonds Enabled by Anthraquinone in Water

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Fig. & Tab. 9

References 21

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