SIOC English
有机化学
高级检索

有机化学 >

0 0

DOI: https://doi.org/10.6023/cjoc202602014

研究论文

可见光促进硝酸铈铵催化芳香羧酸分子内脱氢酯化

  • 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
展开
  • 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,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,绍兴 312000

收稿日期: 2026-02-13

  修回日期: 2026-04-12

  网络出版日期: 2026-06-04

基金资助

国家自然科学基金(No. 21672166 and 21302130 )资助项目.

收起

Visible-Light-Promoted CAN Catalysis Enables Intramolecular Dehydrogenative Lactonization of Aromatic Carboxylic Acids

  • Gaofeng Feng ,
  • Yisha Wang ,
  • Xu-Hong Wang ,
  • Peng-Yu Wang ,
  • Chengan Jin ,
  • Hang Jiang ,
  • Xingcheng Ding ,
  • Tao Cai ,
  • Lemao Yu
Expand
  • a Shangyu College and Zhejiang Key Laboratory of Alternative Technologies for Fine Chemicals Process, Shaoxing University, Shaoxing 312000, P. R. China;
    b Zhejiang Engineering Research Center of Fat-Soluble Vitamin, Shaoxing University, Shaoxing 312000, P.R. China

Received date: 2026-02-13

  Revised date: 2026-04-12

  Online published: 2026-06-04

Supported by

National Natural Science Foundation of China (No. 21672166 and 21302130).

Fold

摘要

本文发展了一种可见光促进硝酸铈铵（CAN）催化的新方法实现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了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; CAN催化; 内酯化反应; 苯并-3,4-香豆素衍生物

本文引用格式

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分子内脱氢酯化[J]. 有机化学, 0 : 0 . DOI: 10.6023/cjoc202602014

Abstract

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/dehalogenation 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; CAN catalysis; lactonization; benzo-3,4-coumarin derivatives

参考文献

[1] For representative reviews: (a) Prier C. K.; Rankic D. A.; Macmillan, D. W. C. Chem. Rev.2013, 113, 5322.(b) Schultz D. M.; Yoon T. P. Science2014, 343, 1239176. (c) Shaw, M. H.; Twilton, J.; Macmillan, D. W. C. J. Org. Chem. 2016, 81, 6898.
[2] For selected examples: (a) King K. A.; Spellane P. J.; Watts, R. J. J. Am. Chem. Soc.1985, 107, 1431.(b) Musacchio, A. J.; Nguyen, L. Q.; Beard, G. H.; Knowles, R. R.J. Am. Chem. Soc. 2014, 136, 12217. (c) Jeffrey, J. L.; Terrett, J. A.; MacMillan, D. W. C. Science 2015, 349, 1532., 1960.
[3] (a) Abderrazak Y.; Bhattacharyya A.; Reiser, O. Angew. Chem., Int. Ed.2021, 60, 21100.(b) Birnthaler, D.; Narobe, R.; Lopez-Berguno, E.; Haag, C.; König, B. ACS Catal. 2023, 13, 1125. , 2915.
[4] (a) Tsurugi H.; Mashima, K. J. Am. Chem. Soc2021, 143, 7879.(b) Chang L.; An Q.; Duan L.; Feng K.; Zuo Z. Chem. Rev.2022, 122, 2429. (c) An, Q; Xing, Y. Y.; Pu, R.; Jia, M.; Chen, Y.; Hu, A.; Zhang, S. Q; Yu, N.; Du, J.; Zhang, Y.; Chen, J.; Liu, W.; Hong, X.; Zuo, Z.J. Am. Chem. Soc. 2023, 145, 359.
[5] (a) Tsui E.; Wang H.; Knowles, R. R. Chem. Sci. 2020, 11, 11124. (b) Chang L.; Wang S.; An Q.; Liu L.; Wang H.; Li Y.; Feng K.; Zuo Z. Chem. Sci.2023, 14, 6841.
[6] (a) Guo J. J.; Hu A.; Chen Y.; Sun J.; Tang H.; Zuo, Z. Angew. Chem. Int. Ed. Engl. 2016, 55, 15319. (b) Müller N.; Stahl J.; Stoiber J.; König, B. Eur. J. Org. Chem.2025, 28. e202500373.
[7] (a) Hu A. H.; Guo J. J.; Pan, H; Zuo, Z. W. Science,2018, 361, 668.(b) Hu, A.; Guo, J. J.; Pan, H.; Tang, H.; Gao, Z.; Zuo, Z. J. Am. Chem. Soc. 2018, 140, 1612-1616. , 486.
[8] (a) Zhang K.; Chang L.; An Q.; Wang X.; Zuo, Z. J. Am. Chem. Soc.2019, 141, 10556-10564.(b) Chen Y.; Wang X.; He X.; An Q.; Zuo, Z. J. Am. Chem. Soc.2021, 143, 4896.
[9] Shirase S.; Tamaki S.; Shinohara K.; Hirosawa K.; Tsurugi H.; Satoh T.; Mashima, K. J. Am. Chem. Soc.2020, 142, 5668.
[10] Li P.; Duan L.; Lin Y.; Chu L.; Zuo, Z. Angew. Chem. Int. Ed. Engl.2025, 64, e202501949.
[11] Zhu X. L.; Chen Y. F.; Zhou, L. N. Org. Lett.2025, 27, 13419.
[12] For selected examples of carboxylic acids as HAT agents: Shan, Y.; Gao F. Q.; Xu C.; Liu H. W.; Tang L.; Zhang J. J.; Wang W.; Chen Z.; Chen Z. Org. Lett.2025, 27, 12223-12229.(b) Qian P.; Zhu D.; Wang X.; Sun Q.; Zhang, S. J. Org. Chem.2024, 89, 6395. (c) Hirose, M.; Sakaguchi, H.; Hashimoto, R.; Furutani, T.; Yamawaki, M.; Suzuki, H.; Yoshimi, Y. Chemistry 2024, 30, e202402285., 9416.
[13] For selected examples of decarboxylation reactions: (a) Li Z.; Wang X.; Xia S.; Jin J. Org. Lett.2019, 21, 4259.(b) Feng G.; Wang X.; Jin, J. Eur. J. Org. Chem.2019, 2019, 6728. (c) Chen, T. Q.; Pedersen, P. S.; Dow, N. W.; Fayad, R.; Hauke, C. E.; Rosko, M. C.; Danilov, E. O.; Blakemore, D. C.; Dechert-Schmitt, A. M.; Knauber, T.; Castellano, F. N.; MacMillan, D. W. C. J. Am. Chem. Soc. 2022, 144, 8296.
[14] (a) Ramirez N. P.; Bosque I.; Gonzalez-Gomez, J. C. Org. Lett.2015, 17, 4550.(b) Yang, Q.; Jia, Z.; Li, L.; Zhang, L.; Luo, S.Org. Chem. Front. 2018, 5, 237.
[15] Morack T.; Metternich J. B.; Gilmour R. Org. Lett.2018, 20, 1316.
[16] Shi G.; Wang Y.; He M.; Yu X.; Bao, M. Org. Chem. Front.2023, 10, 2429.
[17] Sen P. P.; Pathania V.; Raha Roy, S. Org. Chem. Front.2024, 11, 106.
[18] Xia S.; Hu K.; Lei C.; Jin J. Org. Lett.2020, 22, 1385.
[19] Sen P. P.; Raha Roy S. Organometallics2023, 42, 1658.
[20] Wadekar K.; Aswale S.; Yatham, V. R. Org. Biomol. Chem.2020, 18, 983.
[21] Chao M.; Wang F.; Xu L.; Ju Y.; Chen Z.; Wang B.; Gong P.; You J.; Jin M.; Shen D.J. Org. Chem. 2021, 86, 13371.
[22] Feng G.; Zhang C.; He J. Y.; Cai T.; Xu W.; Jin J. Org. Lett.2025, 27, 3501.
[23] Wei C.; Chang D.; Feng N.; Zhan Z.; Shi L. Org. Lett.2025, 27, 2582.
[24] Zhu C.; Zhang Y.; Kan J.; Zhao H.; Su W. Org. Lett.2015, 17, 3418.
[25] Li Y.; Ding Y. J.; Wang J. Y.; Su Y. M.; Wang, X. S. Org. Lett.2013, 15, 2574.
[26] Gao P.; Wei Y. Synthesis2013, 46: 343.
[27] Ramirez N. P.; Bosque I.; Gonzalez-Gomez, J. C. Org. Lett.2015, 17, 4550.
[28] Xia S.; Hu K.; Lei C.; Jin J. Org. Lett.2020, 22, 1385.
[29] Pan, C; Wang L.; Han J. Org. Lett.2020, 22, 4776.
[30] Zhang Y.; Tian Y.; Xiang P.; Huang N.; Wang J.; Xu J. H.; Zhang, M. Org. Biomol. Chem.2016, 14, 9874.
[31] Zhang L.; Zhang Z.; Hong J.; Yu J.; Zhang J.; Mo, F. J. Org. Chem.2018, 83, 3200.
[32] Li J.; Chen H.; Zhang-Negrerie D.; Du Y.; Zhao K. RSC Adv.2013, 3, 4311.
Options
文章导航

/

〈 〉