可见光促进硝酸铈铵催化芳香羧酸的分子内脱氢酯化

doi:10.6023/cjoc202602014

有机化学 ›› 2026, Vol. 46 ›› Issue (10): 4141-4151.DOI: 10.6023/cjoc202602014 上一篇下一篇

研究论文

可见光促进硝酸铈铵催化芳香羧酸的分子内脱氢酯化

冯高峰^a^,^*(), 王怡莎^a, 王旭宏^a, 王鹏宇^a, 金成安^a, 蒋航^a, 丁兴成^a, 蔡涛^b, 余乐茂^a^,^*()

^a 绍兴大学上虞分院精细化工过程替代技术浙江省重点实验室精细化工过程替代技术浙江省重点实验室浙江绍兴 312000
^b 绍兴大学浙江省脂溶性维生素工程技术研究中心浙江省脂溶性维生素工程技术研究中心浙江绍兴 312000

收稿日期:2026-02-13 修回日期:2026-04-12 发布日期:2026-06-03
基金资助:
国家自然科学基金(21672166); 国家自然科学基金(21302130)

Visible-Light-Promoted Ceric Ammonium Nitrate Catalysis Enables the Intramolecular Dehydrogenative Lactonization of Aromatic Carboxylic Acids

Gaofeng Feng^a^,^*(), Yisha Wang^a, Xuhong Wang^a, Pengyu Wang^a, Cheng'an Jin^a, Hang Jiang^a, Xingcheng Ding^a, Tao Cai^b, Lemao Yu^a^,^*()

^a Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, Shangyu College, Shaoxing University, Shaoxing, Zhejiang 312000
^b Zhejiang Engineering Research Center of Fat-Soluble Vitamin, Shaoxing University, Shaoxing, Zhejiang 312000

Received:2026-02-13 Revised:2026-04-12 Published:2026-06-03
Contact:
^* E-mail: chfeng@usx.edu.cn;
yulm@usx.edu.cn;
Supported by:
National Natural Science Foundation of China(21672166); National Natural Science Foundation of China(21302130)

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摘要/Abstract

发展了一种可见光促进硝酸铈铵(CAN)催化的新方法, 实现了芳香羧酸分子内脱氢酯化反应. 该方法先通过可见光促进ArCOO-Ce(IV)络合物的配体金属电荷转移(LMCT)得到酰氧自由基, 该自由基与邻位苯基经分子内环化, C(sp²)—H/X键的脱氢/卤得到内酯产物. 该方法展示了良好的官能团兼容性, 并以优良的产率得到37种不同取代的苯并-3,4-香豆素和4-取代的香豆素衍生物. 该方法操作简单, 试剂便宜易得, 具有良好的潜在应用价值.

关键词: 光催化剂, 硝酸铈铵(CAN)催化, 内酯化反应, 苯并-3,4-香豆素衍生物

A visible-light-mediated ceric ammonium nitrate (CAN) catalyzed protocol for intramolecular lactonization of aromatic carboxylic acids, involving a sequence of acyloxy radical generation via ligand-to-metal charge-transfer (LMCT) of aryl carboxylate-Ce(IV) complex under visible light irradiation, intramolecular cyclization, and dehydrogenation/dehaloge-nation of C(sp²)—H or C(sp²)—X (X=F, Cl, Br) bond, has been developed. A wide range of functional groups could be readily tolerated under this newly developed protocol, and 37 examples of valuable benzo-3,4-coumarin and 4-substituted coumarin derivatives have been conveniently synthesized in good to excellent yields. The protocol features simple operation, employment of cheap and readily available reagents, thus possesses potential practical applications

Key words: photocatalysis, ceric ammonium nitrate (CAN) catalysis, lactonization, benzo-3,4-coumarin derivatives

引用此文

冯高峰, 王怡莎, 王旭宏, 王鹏宇, 金成安, 蒋航, 丁兴成, 蔡涛, 余乐茂. 可见光促进硝酸铈铵催化芳香羧酸的分子内脱氢酯化[J]. 有机化学, 2026, 46(10): 4141-4151.

Gaofeng Feng, Yisha Wang, Xuhong Wang, Pengyu Wang, Cheng'an Jin, Hang Jiang, Xingcheng Ding, Tao Cai, Lemao Yu. Visible-Light-Promoted Ceric Ammonium Nitrate Catalysis Enables the Intramolecular Dehydrogenative Lactonization of Aromatic Carboxylic Acids[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4141-4151.

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Entry	Variations from the standard conditions	Yield^b/%
1	None	82
2	O₂ balloon instead of NaBrO₃	35
3	Na₂S₂O₄; NaIO₄; (NH₄)₂S₂O₈ instead of NaBrO₃	39; 35; 31
4	HFIP; toluene; CH₂Cl₂/H₂O (V/V=1∶1) instead of MeCN	67; 0; 20
5	390 nm Kessil lamp	81
6	440 nm Kessil lamp	80
7	No CAN	20
8	No CAN and no NaBrO₃	10
9	No light	n.r.
10	Under N₂ atmosphere	91
11	90 ℃ bath instead of Kessil lamp	35

Entry	Variations from the standard conditions	Yield^b/%
1	None	82
2	O₂ balloon instead of NaBrO₃	35
3	Na₂S₂O₄; NaIO₄; (NH₄)₂S₂O₈ instead of NaBrO₃	39; 35; 31
4	HFIP; toluene; CH₂Cl₂/H₂O (V/V=1∶1) instead of MeCN	67; 0; 20
5	390 nm Kessil lamp	81
6	440 nm Kessil lamp	80
7	No CAN	20
8	No CAN and no NaBrO₃	10
9	No light	n.r.
10	Under N₂ atmosphere	91
11	90 ℃ bath instead of Kessil lamp	35

可见光促进硝酸铈铵催化芳香羧酸的分子内脱氢酯化

Visible-Light-Promoted Ceric Ammonium Nitrate Catalysis Enables the Intramolecular Dehydrogenative Lactonization of Aromatic Carboxylic Acids

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