电化学催化芳基甲酸脱羧合成多取代三氮唑化合物
Electrochemical Oxidative Decarbonylation of Aromatic Formic Acid for Synthesis of 1,3,5-Trisubstituted 1H-1,2,4-Triazoles
DOI: 10.12677/JOCR.2021.92002, PDF,   
作者: 许甲喆, 周 烨, 曾东文, 何永辉*：云南民族大学民族医药学院，云南 昆明
关键词: 三氮唑；电催化；脱羧；Triazoles； Electrocatalysis； Decarbonylation
摘要: 三氮唑类化合物具有抗炎、抗肿瘤等多种重要的生理活性，合成该类化合物一直是研究热点。本文以四丁基碘化铵为媒介，在电化学条件下实现了芳基甲酸脱羧活化，并与1,3-二取代-1,2,4-三氮唑类化合物发生脱氢交叉偶联反应，以45%~65%的产率得到了1,3,5-三取代-1,2,4-三氮唑类化合物。采用核磁共振和质谱等手段对产物结构进行表征，并提出了可能的反应机理。
Abstract: Triazoles have many important physiological activities such as anti-inflammatory and anti-tumor. Thus, synthesis of these compounds has been a research hotspot. Triazoles have many important physiological activities such as anti-inflammatory and anti-tumor. Thus, synthesis of these com-pounds has been a research hotspot. The electrocatalytic decarbonylation of benzoic acid to con-struct 1,3,5-trisubstituted-1,2,4-triazoles with 1,3-bisubstituted-1,2,4-triazoles was realized in 45%~65% yield at room temperature and without oxidant. The products were confirmed by 1H NMR, 13C NMR, MS and HRMS. The reaction mechanism is proposed.
文章引用：许甲喆, 周烨, 曾东文, 何永辉. 电化学催化芳基甲酸脱羧合成多取代三氮唑化合物[J]. 有机化学研究, 2021, 9(2): 7-12. https://doi.org/10.12677/JOCR.2021.92002

参考文献

[1] Gabor, M. (1986) Anti-Inflammatory and Anti-Allergic Properties of Flavonoids. Progress in Clinical and Biological Research, 213, 471-480.
[2] Singh, G., Singh, L. and Ishar, M.P.S. (2002) 2-(N-Methylanilino)-3-Formylchromone—A Versatile Synthon for Incorporation of Chromone Moiety in a Variety of Heterocyclic Systems and Macrocycles through Reactions with Bifunctional Nucleophiles. Tetrahedron, 58, 7883-7890. [Google Scholar] [CrossRef] 
[3] Martens, S. and Mithofer, A. (2005) Flavones and Flavone Synthases. Phytochemistry, 66, 2399-2407. [Google Scholar] [CrossRef] [PubMed]
[4] Chohan, Z.H., Shaikh, A.U., Rauf, A. and Supuran, C.T. (2006) Antibacterial, Antifungal and Cytotoxic Properties of Novel N-Substituted Sulfonamides from 4-Hydroxycoumarin. Journal of Enzyme Inhibition and Medicinal Chemistry, 21, 741-748. [Google Scholar] [CrossRef] [PubMed]
[5] Djemgou, P.C., Gatsing, D., Tchuendem, M., Ngadjui, B.T., Tane, P., Ahmed, A.A., Gamal-Eldeen, A.M., Adoga, G.I., Hirata, T. and Mabry, T.J. (2006) Antitumor and Immunostimulatory Activity of Two Chromones and Other Constituents from Cassia Petersiana. Natural Product Communications, 1, 961-968. [Google Scholar] [CrossRef] 
[6] Kuroda, M., Uchida, S., Watanabe, K. and Mimaki, Y. (2009) Chromones from the Tubers of Eranthis Cilicica and Their Antioxidant Activity. Phytochemistry, 70, 288-293. [Google Scholar] [CrossRef] [PubMed]
[7] Sandhya, M.B. (2007) Synthesis, Characterization and Pharmacological Activities of Coumarin Devivatives. International Journal of Chemical and Pharmaceutical Sciences, 11, 16-25.
[8] Park, H.J., Kim, J.N., Yoo, H.-J., Wee, K.-R., Kang, S.O., Cho, D.W. and Yoon, U.C. (2013) Rational Design, Synthesis, and Characterization of Deep Blue Phosphorescent Ir(III) Complexes Containing (4’-Substituted-2’-Pyridyl)-1,2,4-Triazole Ancillary Ligands. The Journal of Organic Chemistry, 78, 8054-8064. [Google Scholar] [CrossRef] [PubMed]
[9] Zhang, C., Liang, Z., Jia, X., Wang, M., Zhang, G. and Hu, M.-L. (2020) A Practical Base Mediated Synthesis of 1,2,4-Triazoles Enabled by a Deamination Annulation Strategy. Chemical Communications, 56, 14215-14218. [Google Scholar] [CrossRef] 
[10] Yan, M., Ma, R., Chen, R., Wang, L., Wang, Z. and Ma, Y. (2020) Synthesis of 1,2-Dihydro-1,3,5-Triazine Derivatives via Cu(ii)-Catalyzed C(sp3)–H Activation of N,N-Dimethylethanolamine with Amidines. Chemical Communications, 56, 10946-10949. [Google Scholar] [CrossRef] 
[11] Zhang, L., Tang, D., Gao, J., Wang, J., Wu, P., Meng, X. and Chen, B. (2016) Direct Access to 1,3,5-Trisubstituted 1H-1,2,4-Triazoles from N-Phenylbenzamidines via Copper-Catalyzed Diamination of Aryl Nitriles. Synthesis, 48, 3924-3930. [Google Scholar] [CrossRef] 
[12] Liew, S.K., Holownia, A., Tilley, A.J., Carrera, E.I., Seferos, D.S. and Yudin, A.K. (2016) A Study of Boratriazaroles: An Underdeveloped Class of Heterocycles. The Journal of Organic Chemistry, 81, 10444-10453. [Google Scholar] [CrossRef] [PubMed]
[13] Agisho, H.A., Esatu, H., Hairat, S. and Zaki, M. (2020) TBHP/TBAI–Mediated Simple and Efficient Synthesis of 3,5-Disubstituted and 1,3,5-Trisubstituted 1H-1,2,4-Triazoles via Oxidative Decarbonylation of Aromatic Aldehydes and Testing for Antibacterial Activities. Tetrahedron Letters, 61, Article ID: 151989. [Google Scholar] [CrossRef] 
[14] Li, C.-J. (2009) Cross-dehydrogenative coupling (CDC): Exploring C-C Bond Formations beyond Functional Group Transformations. Accounts of Chemical Research, 42, 335-344. [Google Scholar] [CrossRef] [PubMed]
[15] Yan, M., Kawamata, Y. and Baran, P.S. (2017) Synthetic Organic Electrochemical Methods since 2000: On the Verge of a Renaissance. Chemical Reviews, 117, 13230-13319. [Google Scholar] [CrossRef] [PubMed]
[16] Xiong, P. and Xu, H.-C. (2019) Chemistry with Electrochemically Generated N-Centered Radicals. Accounts of Chemical Research, 52, 3339-3350. [Google Scholar] [CrossRef] [PubMed]
[17] Zeng, L., Li, J., Gao, J., Huang, X., Wang, W., Zheng, X., Gu, L., Li, G., Zhang, S. and He, Y. (2020) An Electrochemical Oxidative Multicomponent Cascade Annulation of Ketones and Amines Used to Produce Imidazoles. Green Chemistry, 22, 3416-3420. [Google Scholar] [CrossRef] 

为你推荐