无催化剂光化学中电子给体–受体(EDA)络合物的作用机制与研究进展
Mechanism and Research Progress of Electron Donor Acceptor (EDA) Complexes in Catalyst Free Photochemistry
DOI: 10.12677/jocr.2026.141012, PDF,   
作者: 曾添晴:浙江师范大学,化学与材料科学学院,浙江 金华
关键词: 无光催化剂EDA络合物自由基反应No Photocatalyst EDA Complex Free Radical Reaction
摘要: 电子给体–受体(EDA)复合物介导的无催化剂光化学反应,凭借无需过渡金属与外加光催化剂、条件温和、绿色高效等优势,近年在合成方法学领域发展迅速,其中由EDA复合物介导的自由基反应备受关注,且在有机合成领域取得了一系列研究进展。本综述以下从核心机理、前沿反应类型、创新策略及应用拓展等方面阐述其研究进展。
Abstract: The catalyst free photochemical reactions mediated by electron donor acceptor (EDA) complexes have developed rapidly in the field of synthetic methodology in recent years, thanks to their advantages of not requiring transition metals and external photocatalysts, mild conditions, and being green and efficient. Among them, the free radical reactions mediated by EDA complexes have attracted much attention and have made a series of research progress in the field of organic synthesis. This review elaborates on the latest developments in core mechanisms, cutting-edge reaction types, innovative strategies, and application expansion.
文章引用:曾添晴. 无催化剂光化学中电子给体–受体(EDA)络合物的作用机制与研究进展[J]. 有机化学研究, 2026, 14(1): 127-141. https://doi.org/10.12677/jocr.2026.141012

参考文献

[1] Qiu, G., Li, Y. and Wu, J. (2016) Recent Developments for the Photoinduced Ar-X Bond Dissociation Reaction. Organic Chemistry Frontiers, 3, 1011-1027. [Google Scholar] [CrossRef
[2] Prier, C.K., Rankic, D.A. and MacMillan, D.W.C. (2013) Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis. Chemical Reviews, 113, 5322-5363. [Google Scholar] [CrossRef] [PubMed]
[3] Chiappe, C. and Pieraccini, D. (2006) Determination of Ionic Liquids Solvent Properties Using an Unusual Probe: The Electron Donor-Acceptor Complex between 4,4’-Bis(Dimethylamino)-Benzophenone and Tetracyanoethene. The Journal of Physical Chemistry A, 110, 4937-4941. [Google Scholar] [CrossRef] [PubMed]
[4] Liu, Z., Gao, S., Hu, M., Zhang, Z., Wei, P. and Zhao, M. (2025) A Visible-Light-Promoted Perfluoroalkylation/Cyclization Cascade Towards Perfluoroalkyl-Substituted Iminoisobenzofurans Using the EDA Complex. Organic & Biomolecular Chemistry, 23, 7576-7583. [Google Scholar] [CrossRef] [PubMed]
[5] Maiti, R., Cauwenbergh, R., Nath, A., Guimarães, A.B.R., Qin, Y., Maseras, F., et al. (2025) EDA Complex‐Driven Desaturation of Heterocyclic Carbonyl Compounds Enabled by HFIP. Angewandte Chemie International Edition, 64, e202514539. [Google Scholar] [CrossRef
[6] Heravi, M.M., Amiri, Z., Kafshdarzadeh, K. and Zadsirjan, V. (2021) Synthesis of Indole Derivatives as Prevalent Moieties Present in Selected Alkaloids. RSC Advances, 11, 33540-33612. [Google Scholar] [CrossRef] [PubMed]
[7] da Silva, G.P., Ali, A., da Silva, R.C., Jiang, H. and Paixão, M.W. (2015) Tris(trimethylsilyl)silane and Visible-Light Irradiation: A New Metal-and Additive-Free Photochemical Process for the Synthesis of Indoles and Oxindoles. Chemical Communications, 51, 15110-15113. [Google Scholar] [CrossRef] [PubMed]
[8] Sun, J., He, Y., An, X., Zhang, X., Yu, L. and Yu, S. (2018) Visible-Light-Induced Iminyl Radical Formation via Electron-Donor-Acceptor Complexes: A Photocatalyst-Free Approach to Phenanthridines and Quinolines. Organic Chemistry Frontiers, 5, 977-981. [Google Scholar] [CrossRef
[9] Yayik, N., Pérez, M., Molins, E., Bosch, J. and Amat, M. (2021) Studies on the Enantioselective Synthesis of E-Ethylidene-Bearing Spiro[Indolizidine-1,3’-Oxindole] Alkaloids. Molecules, 26, Article 428. [Google Scholar] [CrossRef] [PubMed]
[10] Zhu, M., Zhou, K., Zhang, X. and You, S. (2018) Visible-Light-Promoted Cascade Alkene Trifluoromethylation and Dearomatization of Indole Derivatives via Intermolecular Charge Transfer. Organic Letters, 20, 4379-4383. [Google Scholar] [CrossRef] [PubMed]
[11] Hsu, C. and Sundén, H. (2018) α-Aminoalkyl Radical Addition to Maleimides via Electron Donor-Acceptor Complexes. Organic Letters, 20, 2051-2054. [Google Scholar] [CrossRef] [PubMed]
[12] Sahiba, N., Sethiya, A., Soni, J., Agarwal, D.K. and Agarwal, S. (2020) Saturated Five-Membered Thiazolidines and Their Derivatives: From Synthesis to Biological Applications. Topics in Current Chemistry, 378, Article No. 34. [Google Scholar] [CrossRef] [PubMed]
[13] Guo, W., Zhao, M., Tan, W., Zheng, L., Tao, K., Liu, L., et al. (2018) Visible Light-Promoted Three-Component Tandem Annulation for the Synthesis of 2-Iminothiazolidin-4-Ones. The Journal of Organic Chemistry, 83, 1402-1413. [Google Scholar] [CrossRef] [PubMed]
[14] Garbarino, S., Ravelli, D., Protti, S. and Basso, A. (2016) Photoinduced Multicomponent Reactions. Angewandte Chemie International Edition, 55, 15476-15484. [Google Scholar] [CrossRef] [PubMed]
[15] Li, Y., Ma, F., Li, P., Miao, T. and Wang, L. (2019) Hydrogen and Sulfonyl Radical Generation for the Hydrogenation and Arylsulfonylation of Alkenes Driven by Photochemical Activity of Hydrogen Bond Donor‐Acceptor Complexes. Advanced Synthesis & Catalysis, 361, 1606-1616. [Google Scholar] [CrossRef
[16] Seyed Hashtroudi, M., Fathi Vavsari, V. and Balalaie, S. (2022) DABSO as a SO2 Gas Surrogate in the Synthesis of Organic Structures. Organic & Biomolecular Chemistry, 20, 2149-2163. [Google Scholar] [CrossRef] [PubMed]
[17] Mao, R., Yuan, Z., Li, Y. and Wu, J. (2017) n‐Radical‐Initiated Cyclization through Insertion of Sulfur Dioxide under Photoinduced Catalyst‐Free Conditions. ChemistryA European Journal, 23, 8176-8179. [Google Scholar] [CrossRef] [PubMed]
[18] Kandukuri, S.R., Bahamonde, A., Chatterjee, I., Jurberg, I.D., Escudero‐Adán, E.C. and Melchiorre, P. (2014) X‐Ray Characterization of an Electron Donor-Acceptor Complex That Drives the Photochemical Alkylation of Indoles. Angewandte Chemie International Edition, 54, 1485-1489. [Google Scholar] [CrossRef] [PubMed]
[19] Liu, B., Lim, C. and Miyake, G.M. (2017) Visible-Light-Promoted C-S Cross-Coupling via Intermolecular Charge Transfer. Journal of the American Chemical Society, 139, 13616-13619. [Google Scholar] [CrossRef] [PubMed]
[20] Liu, B., Lim, C. and Miyake, G.M. (2018) Light-driven Intermolecular Charge Transfer Induced Reactivity of Ethynylbenziodoxol(on)e and Phenols. Journal of the American Chemical Society, 140, 12829-12835. [Google Scholar] [CrossRef] [PubMed]
[21] Huang, D. and Yan, G. (2017) Recent Advances in Reactions of Azides. Advanced Synthesis & Catalysis, 359, 1600-1619. [Google Scholar] [CrossRef
[22] Shirke, R.P. and Ramasastry, S.S.V. (2017) Organocatalytic β-Azidation of Enones Initiated by an Electron-Donor-Acceptor Complex. Organic Letters, 19, 5482-5485. [Google Scholar] [CrossRef] [PubMed]
[23] Jiang, H., He, Y., Cheng, Y. and Yu, S. (2017) Radical Alkynyltrifluoromethylation of Alkenes Initiated by an Electron Donor-Acceptor Complex. Organic Letters, 19, 1240-1243. [Google Scholar] [CrossRef] [PubMed]
[24] Uenoyama, Y., Fukuyama, T., Morimoto, K., Nobuta, O., Nagai, H. and Ryu, I. (2006) Trifluoromethyl‐Radical‐Mediated Carbonylation of Alkanes Leading to Ethynyl Ketones. Helvetica Chimica Acta, 89, 2483-2494. [Google Scholar] [CrossRef
[25] Xie, J., Li, J., Wurm, T., Weingand, V., Sung, H., Rominger, F., et al. (2016) A General Photoinduced Electron Transfer-Directed Chemoselective Perfluoroalkylation of N, N-Dialkylhydrazones. Organic Chemistry Frontiers, 3, 841-845. [Google Scholar] [CrossRef
[26] Sladojevich, F., McNeill, E., Börgel, J., Zheng, S. and Ritter, T. (2015) Condensed‐Phase, Halogen‐Bonded CF3I and C2F5I Adducts for Perfluoroalkylation Reactions. Angewandte Chemie International Edition, 54, 3712-3716. [Google Scholar] [CrossRef] [PubMed]
[27] Yu, J. and Cai, C. (2017) Ambient-Light-Promoted Perfluoroalkylative Cyclization of β, γ‐Unsaturated Hydrazones: Synthesis of Perfluoroalkylated Pyrazolines. European Journal of Organic Chemistry, 2017, 6008-6012. [Google Scholar] [CrossRef
[28] Sun, X., Wang, W., Li, Y., Ma, J. and Yu, S. (2016) Halogen-Bond-Promoted Double Radical Isocyanide Insertion under Visible-Light Irradiation: Synthesis of 2-Fluoroalkylated Quinoxalines. Organic Letters, 18, 4638-4641. [Google Scholar] [CrossRef] [PubMed]
[29] Woźniak, Ł., Murphy, J.J. and Melchiorre, P. (2015) Photo-Organocatalytic Enantioselective Perfluoroalkylation of β-Ketoesters. Journal of the American Chemical Society, 137, 5678-5681. [Google Scholar] [CrossRef] [PubMed]
[30] Mulliken, R.S. (1952) Molecular Compounds and Their Spectra. II. Journal of the American Chemical Society, 74, 811-824. [Google Scholar] [CrossRef
[31] Foster, R. (1960) The Absorption Spectra of Molecular Complexes. Tetrahedron, 10, 96-101. [Google Scholar] [CrossRef
[32] Marcus, R.A. (1956) On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. I. The Journal of Chemical Physics, 24, 966-978. [Google Scholar] [CrossRef
[33] El-Zaria, M.E. (2008) Spectrophotometric Study of the Charge Transfer Complexation of Some Porphyrin Derivatives as Electron Donors with Tetracyanoethylene. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 69, 216-221. [Google Scholar] [CrossRef] [PubMed]
[34] Saleem, L.M.N., Al-Hyali, E.A.S. and Al-Taei, F.H.M. (2012) Spectral and Theoretical Studies of the Stability Constant of Charge Transfer Complexes of a Number of Schiff Bases with Eu(Fod)3 in Different Solvents. Oriental Journal of Chemistry, 28, 1171-1178. [Google Scholar] [CrossRef
[35] Pal, P., Bhattacharya, S., Mukherjee, A.K. and Mukherjee, D.C. (2005) Absorption Spectrometric and Thermodynamic Study of Charge Transfer Complexes of Menadione (Vitamin K3) with a Series of Phenols. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 61, 879-885. [Google Scholar] [CrossRef] [PubMed]
[36] Teleb, S.M., El-korashy, S.A., Ali, M.M. and Gaballa, A.S. (2020) Chemical and Biological Studies on Charge-Transfer Complexes of Cimetidine with Various Electron Acceptors. Journal of Molecular Structure, 1202, Article ID: 127256. [Google Scholar] [CrossRef
[37] Nakagawa, A., Ito, A., Sakuda, E., Fujii, S. and Kitamura, N. (2018) Emission Tuning of Heteroleptic Arylborane-Ruthenium(II) Complexes by Ancillary Ligands: Observation of Strickler-Berg-Type Relation. Inorganic Chemistry, 57, 9055-9066. [Google Scholar] [CrossRef] [PubMed]
[38] Ko, Y.H., Kim, K., Kim, E. and Kim, K. (2007) Exclusive Formation of 1:1 and 2:2 Complexes between Cucurbit[8]Uril and Electron Donor-Acceptor Molecules Induced by Host-Stabilized Charge-Transfer Interactions. Supramolecular Chemistry, 19, 287-293. [Google Scholar] [CrossRef
[39] Strelnikov, A.A., Konev, A.S., Levin, O.V., Khlebnikov, A.F., Iwasaki, A., Yamanouchi, K., et al. (2020) Switching Competition between Electron and Energy Transfers in Porphyrin-Fullerene Dyads. The Journal of Physical Chemistry B, 124, 10899-10912. [Google Scholar] [CrossRef] [PubMed]
[40] Nampally, V., Palnati, M.K., Baindla, N., Varukolu, M., Gangadhari, S. and Tigulla, P. (2022) Charge Transfer Complex between o-Phenylenediamine and 2, 3-Dichloro-5, 6-Dicyano-1, 4-Benzoquinone: Synthesis, Spectrophotometric, Characterization, Computational Analysis, and Its Biological Applications. ACS Omega, 7, 16689-16704. [Google Scholar] [CrossRef] [PubMed]
[41] Agatić, Z.F., Tepavčević, V., Puača, G. and Poša, M. (2024) Interaction of Drug Molecules with Surfactants Below (Benesi-Hildebrand Equation) and above the Critical Micelle Concentration (Kawamura Equation). International Journal of Pharmaceutics, 665, Article ID: 124675. [Google Scholar] [CrossRef] [PubMed]
[42] Bao, L., Wang, B., Yu, P., Huang, C., Pan, C., Fang, H., et al. (2019) Intermolecular Packing and Charge Transfer in Metallofullerene/Porphyrin Cocrystals. Chemical Communications, 55, 6018-6021. [Google Scholar] [CrossRef] [PubMed]
[43] Knyazev, A.A., Krupin, A.S. and Galyametdinov, Y.G. (2022) Luminescence Behavior of PMMA Films Doped with Tb(III) and Eu(III) Complexes. Journal of Luminescence, 242, Article ID: 118609. [Google Scholar] [CrossRef
[44] Aloisi, G.G. and Pignataro, S. (1973) Molecular Complexes of Substituted Thiophens with σ and π Acceptors. Charge Transfer Spectra and Ionization Potentials of the Donors. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 69, 534-539. [Google Scholar] [CrossRef
[45] Alghanmi, R.M. (2013) Spectrophotometric Study of Charge Transfer Complex between 2,6-Diaminopyridine and 2,5-Dihydroxy-p-Benzoquinone. Physics and Chemistry of Liquids, 51, 365-380. [Google Scholar] [CrossRef
[46] Cui, Z., Aquino, A.J.A., Sue, A.C.-. and Lischka, H. (2018) Analysis of Charge Transfer Transitions in Stacked π-Electron Donor-Acceptor Complexes. Physical Chemistry Chemical Physics, 20, 26957-26967. [Google Scholar] [CrossRef] [PubMed]
[47] Nour, E., AlQaradawi, S.Y., Mostafa, A., Shams, E. and Bazzi, H.S. (2010) Synthesis, Characterization and Spectroscopic Structural Studies of Charge-Transfer Complexes of 1,4,8,11-Tetraazacyclotetradecane-5,7-Dione with Iodine, TCNE and DDQ. Journal of Molecular Structure, 980, 218-224. [Google Scholar] [CrossRef
[48] Bhattacharya, S., Banerjee, M. and Mukherjee, A.K. (2003) Spectrophotometric and Thermodynamic Studies of [60]Fullerene/Methylbenzene Charge Transfer Complexes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 59, 3147-3158. [Google Scholar] [CrossRef] [PubMed]
[49] Khan, I.M., Alam, K., Alam, M.J. and Ahmad, M. (2019) Spectrophotometric and Photocatalytic Studies of H-Bonded Charge Transfer Complex of Oxalic Acid with Imidazole: Single Crystal XRD, Experimental and DFT/TD-DFT Studies. New Journal of Chemistry, 43, 9039-9051. [Google Scholar] [CrossRef
[50] Devore, D.P., Ellington, T.L. and Shuford, K.L. (2024) Elucidating the Role of Electron-Donating Groups in Halogen Bonding. The Journal of Physical Chemistry A, 128, 1477-1490. [Google Scholar] [CrossRef] [PubMed]