MCM-41@FeCl3催化吲哚与烯酰胺的Friedel-Crafts烷基化反应：一种可回收的高区域选择性体系
MCM-41@FeCl3 for the Friedel-Crafts Alkylation of Indoles with Enamides: A Recyclable System toward Highly Regioselective Products
DOI: 10.12677/jocr.2025.134036, PDF,   
作者: 晋海洋, 张永飞, 惠永海*：岭南师范学院化学化工学院，清洁能源材料化学广东普通高校重点实验室，广东 湛江
关键词: MCM-41；固载催化剂；吲哚；烯酰胺；傅克反应；MCM-41； Immobilized Solid Catalyst； Indole； Enamide； Friedel-Crafts Reaction
摘要: 基于有序介孔材料固有的限域效应与高比表面积特性，其所固载的催化剂能够协同实现活性位点的高效利用与反应传质过程的显著强化。本研究采用MCM-41固载FeCl₃催化剂，成功应用于吲哚与烯酰胺的Friedel-Crafts烷基化反应，从而高效、高区域选择性地合成了一系列含双生物碱骨架的吲哚酰胺类化合物，收率最高可达99%。此外，该催化体系展现出优异的稳定性，在连续五次循环使用后，其催化活性未出现显著下降。
Abstract: Leveraging the inherent confinement effect and high specific surface area of ordered mesoporous materials, the supported catalysts enable the synergistic enhancement of active site utilization and reaction mass transfer. In this study, an MCM-41-supported FeCl₃ catalyst was successfully applied to the Friedel-Crafts alkylation of indoles with enamides. This strategy afforded a series of indole-amide compounds incorporating bis-alkaloid scaffolds with high efficiency and remarkable regioselectivity, achieving yields of up to 99%. Furthermore, the catalytic system demonstrated excellent stability, maintaining its activity without significant loss over five consecutive reaction cycles.
文章引用：晋海洋, 张永飞, 惠永海. MCM-41@FeCl3催化吲哚与烯酰胺的Friedel-Crafts烷基化反应：一种可回收的高区域选择性体系[J]. 有机化学研究, 2025, 13(4): 372-379. https://doi.org/10.12677/jocr.2025.134036

参考文献

[1] Silva Moratório de Moraes, R., Mestre Botelho, A.B., Tavares de Almeida Pinto, G., Couto Rodrigues, S., Miranda Martins, M.T., Alves Soares, D.L., et al. (2025) Chemistry, Applications, and Synthesis Methods of Indole Derivatives: A Comprehensive Review. The Chemical Record. [Google Scholar] [CrossRef] 
[2] Zeng, W., Han, C., Mohammed, S., Li, S., Song, Y., Sun, F., et al. (2024) Indole-Containing Pharmaceuticals: Targets, Pharmacological Activities, and SAR Studies. RSC Medicinal Chemistry, 15, 788-808. [Google Scholar] [CrossRef] [PubMed]
[3] Li, W., Xu, Q., Miao, Q. and Xiao, B. (2024) Dual Photoredox/Nickel Catalysis Enables Diastereoselective Synthesis of Multisubstituted γ-Lactams Using Alkyl-GeMe3 as Radical Precursors. The Journal of Organic Chemistry, 89, 16269-16281. [Google Scholar] [CrossRef] [PubMed]
[4] Teng, H., Huang, H. and Wang, C. (2012) Catalytic Asymmetric Construction of Spiro(γ‐Butyrolactam‐γ‐Butyrolactone) Moieties through Sequential Reactions of Cyclic Imino Esters with Morita-Baylis-Hillman Bromides. Chemistry—A European Journal, 18, 12614-12618. [Google Scholar] [CrossRef] [PubMed]
[5] Kenda, B., Quesnel, Y., Ates, A., Michel, P., Turet, L. and Mercier, J. (2006) 2-Oxo-1-Pyrrolidine Derivatives, Processes for Preparing Them and Their Therapeutic Use on the Central Nervous System. WO2006128693A1. 2006-07-12.
[6] Jiang, R., Wu, X., Zhu, X., Xu, X. and Ji, S. (2010) Ferric(III) Nitrate: An Efficient Catalyst for the Regioselective Friedel-Crafts Reactions of Indoles and Tert‐Enamides in Water. European Journal of Organic Chemistry, 31, 5946-5950. [Google Scholar] [CrossRef] 
[7] Niu, T., Huang, L., Wu, T. and Zhang, Y. (2011) FeCl3-Promoted Alkylation of Indoles by Enamides. Organic & Biomolecular Chemistry, 9, 273-277. [Google Scholar] [CrossRef] [PubMed]
[8] Huo, C., Kang, L., Xu, X., Jia, X., Wang, X., Xie, H., et al. (2014) Triarylaminium Salt Facilitated Friedel-Crafts Reaction of Indoles with Enamides and Vinyl Ethers. Tetrahedron Letters, 55, 954-958. [Google Scholar] [CrossRef] 
[9] Jia, Y., Zhong, J., Zhu, S., Zhang, C. and Zhou, Q. (2007) Chiral Brønsted Acid Catalyzed Enantioselective Friedel-Crafts Reaction of Indoles and Α‐aryl Enamides: Construction of Quaternary Carbon Atoms. Angewandte Chemie International Edition, 46, 5565-5567. [Google Scholar] [CrossRef] [PubMed]
[10] Xu, X., Ji, S., Zhang, Y., Jiang, J., Chu, X., Jiang, R., et al. (2012) Friedel-Crafts Alkylation of Indoles by Tert-Enamides in Acetic Acid. Synlett, 23, 751-754. [Google Scholar] [CrossRef] 
[11] Xu, H., Zi, Y., Xu, X., Wang, S. and Ji, S. (2013) TFA-Catalyzed C-N Bond Activation of Enamides with Indoles: Efficient Synthesis of 3,3-Bisindolylpropanoates and Other Bisindolylalkanes. Tetrahedron, 69, 1600-1605. [Google Scholar] [CrossRef] 
[12] Chu, X., Wang, S. and Ji, S. (2013) Recyclable NaHSO4 Catalyzed Alkylation of Tert-Enamides with Indoles or Amines in Water: Facile Construction of Pharmaceutically Analogous Bis-Alkaloid Scaffolds. RSC Advances, 3, 8380-8387. [Google Scholar] [CrossRef] 
[13] 李建鹏, 张世奇, 高天明, 张永飞, 王赟, 夏加亮, 韩冰, 惠永海. 磷钼酸室温催化吲哚与 1-乙烯基吡咯烷-2-酮的傅克反应研究[J]. 有机化学研究, 2019, 7(4): 103-108.
[14] Jiang, R., Xu, H., Xu, X., Chu, X. and Ji, S. (2011) Direct Alkylation of Indoles and Amines by Tert-Enamides: Facile Access to Pharmaceutically Active 2-Oxo-1-Pyrrolidine Analogues. Organic & Biomolecular Chemistry, 9, 5659-5669. [Google Scholar] [CrossRef] [PubMed]
[15] Hui, Y., Xia, J., Li, J., Wang, Y. and Zhang, Y. (2022) Ionic Liquid-Functional MCM-41 as a High Effective Catalyst for the Synthesis of Isatylidene Malononitrile via Knoevenagel Condensation. Journal of Saudi Chemical Society, 26, Article ID: 101399. [Google Scholar] [CrossRef] 
[16] Hui, Y., Li, J., Yu, B., Xing, X., Gao, T., Qian, X., et al. (2022) Amine-Functionalized MCM-41 as an Efficient Catalyst for the Synthesis of Sulfur/Dinitrogen-Fused Heterocycles via [3 + 3] Cycloaddition in Water. New Journal of Chemistry, 46, 6804-6810. [Google Scholar] [CrossRef] 
[17] Hui, Y., Zhang, Y., Li, J., Yu, B., Han, B., Wang, Y., et al. (2021) One-Pot Synthesis of Spiro[Indoline-3,2’-Pyrrolidin]-Ones Catalyzed by Mesoporous Molecular Sieve MCM-41. Tetrahedron, 93, Article ID: 132283. [Google Scholar] [CrossRef] 
[18] Hui, Y., Zhang, Y., Luo, Y., Li, J., Wang, Y., Gao, T., et al. (2020) Facile Synthesis of Spiro Thiazolidinone via Cyclic Ketones, Amines and Thioglycolic Acid by MCM-41-Schiff Base-CuSO₄∙5H₂O. Research on Chemical Intermediates, 47, 521-532. [Google Scholar] [CrossRef] 
[19] 刘雪松, 于顺明. 固载化FeCl3催化合成螺环苯并吡喃[2, 3-b]吲哚类衍生物[J]. 有机化学研究, 2020, 8(2): 15-23.

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