分子内环化反应合成芴类化合物的研究进展
Research Progress on the Synthesis of Fluorene Compounds through Intramolecular Cyclization Reactions
摘要: 芴是一种共轭良好的平面多环芳香有机化合物，具有特殊的物理和化学性质，是有机合成中的重要支架。芴类化合物在聚合物、电子设备、传感器和光致变色材料中被广泛应用，因此芴及其衍生物的合成方法具有重要的研究价值。在本文中，主要综述了芴类化合物的结构特征和应用前景，然后对近年来通过分子内环化反应合成芴类化合物的方法进行了总结和归纳，为此类化合物的合成研究提供参考。
Abstract: Fluorene is a well-conjugated planar polycyclic aromatic organic compound with special physical and chemical properties, making it an important scaffold in organic synthesis. Fluorene derivatives are widely used in polymers, electronic devices, sensors, and photochromic materials, hence, the synthesis methods of fluorene and its derivatives hold significant research value. This article primarily reviews the structural characteristics and application prospects of fluorene compounds, and summarizes the methods for synthesizing fluorene compounds through intramolecular cyclization reactions in recent years, providing a reference for the synthesis research of these compounds.
文章引用：张怡, 薛梓超, 赵凯丽, 邓雪帆, 樊晓辉. 分子内环化反应合成芴类化合物的研究进展[J]. 材料化学前沿, 2025, 13(3): 396-406. https://doi.org/10.12677/amc.2025.133041

参考文献

[1] Burns, D.M. and Iball, J. (1955) The Crystal and Molecular Structure of Fluorene. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 227, 200-214. [Google Scholar] [CrossRef] 
[2] Grimsdale, A.C. and Müllen, K. (2007) Oligomers and Polymers Based on Bridged Phenylenes as Electronic Materials. Macromolecular Rapid Communications, 28, 1676-1702. [Google Scholar] [CrossRef] 
[3] Shi, Y. and Gao, S. (2016) Recent Advances of Synthesis of Fluorenone and Fluorene Containing Natural Products. Tetrahedron, 72, 1717-1735. [Google Scholar] [CrossRef] 
[4] InganÄs, O., Zhang, F. and Andersson, M.R. (2009) Alternating Polyfluorenes Collect Solar Light in Polymer Photovoltaics. Accounts of Chemical Research, 42, 1731-1739. [Google Scholar] [CrossRef] [PubMed]
[5] Saragi, T.P., Spehr, T., Siebert, A., Fuhrmann-Lieker, T. and Salbeck, J. (2007) Spiro Compounds for Organic Optoelectronics. Chemical Reviews, 107, 1011-1065. [Google Scholar] [CrossRef] [PubMed]
[6] Fleckenstein, C.A. and Plenio, H. (2007) 9-Fluorenylphosphines for the Pd-Catalyzed Sonogashira, Suzuki, and Buchwald-Hartwig Coupling Reactions in Organic Solvents and Water. Chemistry—A European Journal, 13, 2701-2716. [Google Scholar] [CrossRef] [PubMed]
[7] Wertz, S., Leifert, D. and Studer, A. (2013) Cross Dehydrogenative Coupling via Base-Promoted Homolytic Aromatic Substitution (BHAS): Synthesis of Fluorenones and Xanthones. Organic Letters, 15, 928-931. [Google Scholar] [CrossRef] [PubMed]
[8] Morimoto, K., Itoh, M., Hirano, K., Satoh, T., Shibata, Y., Tanaka, K. and Miura, M. (2012) Synthesis of Fluorene Derivatives through Rhodium‐Catalyzed Dehydrogenative Cyclization. Angewandte Chemie International Edition, 51, 5359-5362. [Google Scholar] [CrossRef] [PubMed]
[9] Itoh, M., Hirano, K., Satoh, T., Shibata, Y., Tanaka, K. and Miura, M. (2013) Rhodium-and Iridium-Catalyzed Dehydrogenative Cyclization through Double C-H Bond Cleavages to Produce Fluorene Derivatives. The Journal of Organic Chemistry, 78, 1365-1370. [Google Scholar] [CrossRef] [PubMed]
[10] Song, J., Li, Y., Sun, W., Yi, C., Wu, H., Wang, H. and Liu, C. (2016) Efficient Palladium-Catalyzed C (sp 2)-H activation towards the Synthesis of Fluorenes. New Journal of Chemistry, 40, 9030-9033. [Google Scholar] [CrossRef] 
[11] Corrie, T.J.A., Ball, L.T., Russell, C.A. and Lloyd-Jones, G.C. (2016) Au-Catalyzed Biaryl Coupling to Generate 5-to 9-Membered Rings: Turnover-Limiting Reductive Elimination versus Π-complexation. Journal of the American Chemical Society, 139, 245-254. [Google Scholar] [CrossRef] [PubMed]
[12] Fuchibe, K. and Akiyama, T. (2006) Low-Valent Niobium-Mediated Double Activation of C-F/C-H Bonds: Fluorene Synthesis from o-Arylated Α, α,α-Trifluorotoluene Derivatives. Journal of the American Chemical Society, 128, 1434-1435. [Google Scholar] [CrossRef] [PubMed]
[13] Hwang, S.J., Kim, H.J. and Chang, S. (2009) Highly Efficient and Versatile Synthesis of Polyarylfluorenes via Pd-Catalyzed C-H Bond Activation. Organic Letters, 11, 4588-4591. [Google Scholar] [CrossRef] [PubMed]
[14] Chernyak, N. and Gevorgyan, V. (2009) Synthesis of Fluorenes via the Palladium-Catalyzed 5-Exo-Dig Annulation of o-Alkynylbiaryls. Advanced Synthesis & Catalysis, 351, 1101-1114. [Google Scholar] [CrossRef] [PubMed]
[15] Hsiao, C., Lin, Y., Liu, C., Wu, T. and Wu, Y. (2010) Synthesis of Methylene-Bridge Polyarenes through Palladium-Catalyzed Activation of Benzylic Carbon-Hydrogen Bond. Advanced Synthesis & Catalysis, 352, 3267-3274. [Google Scholar] [CrossRef] 
[16] Sarkar, S., Maiti, S., Bera, K., Jalal, S. and Jana, U. (2012) Highly Efficient Synthesis of Polysubstituted Fluorene via Iron-Catalyzed Intramolecular Friedel-Crafts Alkylation of Biaryl Alcohols. Tetrahedron Letters, 53, 5544-5547. [Google Scholar] [CrossRef] 
[17] Hirano, M., Kawazu, S. and Komine, N. (2014) Direct Access to Fluorene by Successive C-O/C-H Bond Activations of 2-Phenylbenzyl Ester. Organometallics, 33, 1921-1924. [Google Scholar] [CrossRef] 
[18] Das, T., Chakraborty, A. and Sarkar, A. (2014) Solvent Control of Product Diversity in Palladium-Catalyzed Addition of Arylboronic Acid to Aryl Aldehydes. Tetrahedron Letters, 55, 5174-5178. [Google Scholar] [CrossRef] 
[19] Aziz, J., Frison, G., Gómez, M., Brion, J., Hamze, A. and Alami, M. (2014) Copper-Catalyzed Coupling of n-Tosylhydrazones with Amines: Synthesis of Fluorene Derivatives. ACS Catalysis, 4, 4498-4503. [Google Scholar] [CrossRef] 
[20] Seo, B., Jeon, W.H., Kim, J., Kim, S. and Lee, P.H. (2014) Synthesis of Fluorenes via Tandem Copper-Catalyzed [3+2] Cycloaddition and Rhodium-Catalyzed Denitrogenative Cyclization in a 5-Exo Mode from 2-Ethynylbiaryls and n-Sulfonyl Azides in One Pot. The Journal of Organic Chemistry, 80, 722-732. [Google Scholar] [CrossRef] [PubMed]
[21] Huang, D., Yang, W., Zhang, J., Wang, X., Wang, X. and Hu, Y. (2016) Lewis Acid-Catalyzed Tandem Synthesis of 9-Sulfonylamino-and 9-Arylfluorenes. RSC Advances, 6, 47570-47578. [Google Scholar] [CrossRef] 
[22] Xu, S., Chen, R., Fu, Z., Zhou, Q., Zhang, Y. and Wang, J. (2017) Palladium-Catalyzed Formal [4+1] Annulation via Metal Carbene Migratory Insertion and C (sp2)-H Bond Functionalization. ACS Catalysis, 7, 1993-1997. [Google Scholar] [CrossRef] 
[23] Tanji, Y., Tsuji, Y. and Fujihara, T. (2020) Palladium-Catalyzed Synthesis of Fluorenes by Intramolecular C (sp2)-H Activation at Room Temperature. Synlett, 31, 805-808. [Google Scholar] [CrossRef] 
[24] Guo, H., Zhang, S., Feng, X., et al. (2022) Palladium-Catalyzed Cycloisomerization of 2-Ethynylbiaryls to 9-Methylidene Fluorenes. Organic Letters, 24, 2596-2600. [Google Scholar] [CrossRef] [PubMed]
[25] Matsuyama, H., Zhang, X., Terada, M., et al. (2023) Construction of Alkylidene Fluorene Scaffolds Using Pd-Catalyzed Direct Arene/Alkene Coupling Strategy. Organic Letters, 25, 800-804. [Google Scholar] [CrossRef] [PubMed]