有机染料催化苄基C—H键的有氧光氧化

doi:10.6023/cjoc202601037

摘要/Abstract

在光催化剂曙红Y的介导下, 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地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、合成实用性突出等优点. 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4,4'-二甲氧基苯酚酯(hCECE)抑制剂. 此外, 对反应机理以及曙红Y的光物理性质开展了系统研究.

关键词: 光催化, 曙红Y, 苄基C(sp³)—H, 醛, 酮

Photooxygenation of benzylic C(sp³)—H bonds by oxygen occurs efficiently under photoirradiation using Eosin Y as a photocatalyst to yield aldehydes and ketones. This method is able to activate alkylarenes such as toluene and can overcome overoxidation into carboxylic acids. This approach features an inexpensive 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: photocatalysis, Eosin Y, benzylic C(sp³)—H, aldehyde, ketone

引用此文

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, 2026, 46(10): 4172-4181.

Wenjing Li, Chunye Liu, Lingling Liang, Yanqing Miao, Jing You, Siyu Shen. Organic Dye-Catalyzed Aerobic Photooxidation of Benzylic C—H Bonds[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4172-4181.

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图/表 11

Figure 1. Examples of prodrugs containing ketone moiety

Scheme 1. Methodologies for the oxidative benzylic C(sp3)—H bond

Entry	Wavelength/nm	Photocatalyst	Oxidant	Yield/%
1	365	Fluorescein	TBHP	Trace
2	365	Na₂-Eosin Y	TBHP	50
3	365	Rhodamine 6G	TBHP	37
4	365	Rhodamine B	TBHP	Trace
5	365	Dibromofluorescein	TBHP	44
6	365	Eosin Y	TBHP	65
7	365	Eosin Y	O₂	36
8	365	Eosin Y	Air	20
9^c	365	Eosin Y	TBHP	76
10	365	—	TBHP	n.d.
11	390	Eosin Y	TBHP	44
12	425	Eosin Y	TBHP	31
13	450	Eosin Y	TBHP	24

Table 1. Optimization of reaction conditionsa,b

Table 2. Photocatalytic oxidative benzylic C(sp3)—H to aldehydesa,b

Table 3. Photocatalytic oxidative benzylic C(sp3)—H to ketonesa,b

Scheme 2. Scale-up reaction and synthesis applications

Scheme 3. Isotope-labelling experiments

Scheme 4. Control experiments

Figure 2. On/off experiments

Figure 3. (a) Fluorescence quenching of excited Eosin Y by toluene S1 in CH3CN; (b) Stern-Volmer plots for the fluorescence quenching of Eosin Y with toluene

Scheme 5. Proposed mechanism

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