羰基脱氧官能团化反应研究进展
Research Progress on Carbonyl Deoxygenation Functionalization Reactions
DOI: 10.12677/jocr.2026.141004, PDF,   
作者: 张学梅:浙江师范大学化学与材料科学学院,浙江 金华
关键词: 羰基脱氧策略官能团化Carbonyl Deoxygenation Strategy Functionalization
摘要: 醛、酮等羰基化合物在自然界中广泛存在,种类繁多,结构与功能各异,是廉价易得的化学化工原料。由于强C=O双键的同时裂解与转化具有很强的挑战性,通常需要特定的反应条件和试剂,且部分反应难以实现。近年来醛、酮脱氧领域迅速发展,脱氧官能团化方法日益进步。本文系统总结了醛、酮脱氧官能团化方法的发展和面临的挑战,为羰基脱氧官能团化的突破提供参考。
Abstract: Carbonyl compounds such as aldehydes and ketones are widely present in nature, with a wide variety of types, diverse structures, and functions, and serve as inexpensive and readily available chemical and industrial raw materials. Due to the strong C=O double bond, simultaneous cleavage and transformation present significant challenges, usually requiring specific reaction conditions and reagents, and some reactions are difficult to achieve. In recent years, the field of aldehyde and ketone deoxygenation has developed rapidly, and methods for deoxygenation functionalization have been steadily improving. This article systematically summarizes the development and challenges of aldehyde and ketone deoxygenation functionalization methods, providing a reference for breakthroughs in carbonyl deoxygenation functionalization.
文章引用:张学梅. 羰基脱氧官能团化反应研究进展[J]. 有机化学研究, 2026, 14(1): 42-53. https://doi.org/10.12677/jocr.2026.141004

参考文献

[1] Barluenga, J., Tomás-Gamasa, M., Aznar, F. and Valdés, C. (2009) Metal-Free Carbon-Carbon Bond-Forming Reductive Coupling between Boronic Acids and Tosylhydrazones. Nature Chemistry, 1, 494-499. [Google Scholar] [CrossRef
[2] Dai, X.J., Li, C.C. and Li, C.J. (2021) Carbonyl Umpolung as an Organometallic Reagent Surrogate. Chemical Society Reviews, 50, 10733-10742. [Google Scholar] [CrossRef
[3] Li, J., Huang, C.Y. and Li, C.J. (2022) Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids. Angewandte Chemie International Edition, 61, e202112770. [Google Scholar] [CrossRef
[4] Ertl, P. and Schuhmann, T. (2019) A Systematic Cheminformatics Analysis of Functional Groups Occurring in Natural Products. Journal of Natural Products, 82, 1258-1263. [Google Scholar] [CrossRef
[5] Han, J.S., Kang, S., Jung, I.N. and Yoo, B.R. (2016) Deoxygenative Silylation of Aromatic Carbonyl Compounds with Hsicl 3 in the Presence of Quaternary Phosphonium Chloride: A Facile Route to Arylmethyltrichlorosilane Journal of Industrial and Engineering Chemistry, 42, 157-161. [Google Scholar] [CrossRef
[6] Hu, X.Q., Hou, Y.X., Liu, Z.K. and Gao, Y. (2020) Recent Advances in Phosphoranyl Radical-Mediated Deoxygenative Functionalisation. Organic Chemistry Frontiers, 7, 2319-2324. [Google Scholar] [CrossRef
[7] Rossi-Ashton, J.A., Clarke, A.K., Unsworth, W.P. and Taylor, R.J.K. (2020) Phosphoranyl Radical Fragmentation Reactions Driven by Photoredox Catalysis. ACS Catalysis, 10, 7250-7261. [Google Scholar] [CrossRef
[8] Sun, W., Wang, L., Xia, C. and Liu, C. (2018) Dual Functionalization of A-Monoboryl Carbanions through Deoxygenative Enolization with Carboxylic Acids. Angewandte Chemie International Edition, 57, 5501-5505. [Google Scholar] [CrossRef
[9] Kerr, J.A. (1966) Bond Dissociation Energies by Kinetic Methods. Chemical Reviews, 66, 465-500. [Google Scholar] [CrossRef
[10] Nicewicz, D., Roth, H. and Romero, N. (2015) Experimental and Calculated Electrochemical Potentials of Common Organic Molecules for Applications to Single-Electron Redox Chemistry. Synlett, 27, 714-723. [Google Scholar] [CrossRef
[11] Zheng, P., Xu, W., Wang, H., Wang, D., Wu, X. and XU, T. (2022) Deoxygenative Arylboration of Aldehydes via Copper and Nickel/Photoredox Catalysis. ACS Catalysis, 12, 14926-14933. [Google Scholar] [CrossRef
[12] Luo, Y., Huang, G., Ding, K., Xue, X. and Wang, X. (2025) Oxygen Transposition of Formamide to Α-Aminoketone Moiety in a Carbene-Initiated Domino Reaction. Nature Chemistry, 17, 1196-1206. [Google Scholar] [CrossRef
[13] Savela, R., Wärnå, J., Murzin, D.Y. and Leino, R. (2015) Iron Catalyzed Halogenation of Benzylic Aldehydes and Ketones. Catalysis Science & Technology, 5, 2406-2417. [Google Scholar] [CrossRef
[14] Gellert, B.A., Kahlcke, N., Feurer, M. and Roth, S. (2011) Triflic Acid Catalyzed Reductive Coupling Reactions of Carbonyl Compounds with O-, S-, and N-Nucleophiles. Chemistry—A European Journal, 17, 12203-12209. [Google Scholar] [CrossRef
[15] Petronilho, A., Vivancos, A. and Albrecht, M. (2017) Ether Formation through Reductive Coupling of Ketones or Aldehydes Catalyzed by a Mesoionic Carbene Iridium Complex. Catalysis Science & Technology, 7, 5766-5774. [Google Scholar] [CrossRef
[16] Melvin, P.R., Ferguson, D.M., Schimler, S.D., Bland, D.C. and Sanford, M.S. (2019) Room Temperature Deoxyfluorination of Benzaldehydes and α-Ketoesters with Sulfuryl Fluoride and Tetramethylammonium Fluoride. Organic Letters, 21, 1350-1353. [Google Scholar] [CrossRef
[17] Liu, Y., Xu, X. and Qing, F. (2020) Deoxygenative 1,1-Bis-Trifluoromethylthiolation of Aromatic Aldehydes to Access Bis(trifluoromethylthio) Methylarenes. Advanced Synthesis & Catalysis, 362, 5031-5035. [Google Scholar] [CrossRef
[18] Chen, J., Lin, J. and Xiao, J. (2018) Halogenation through Deoxygenation of Alcohols and Aldehydes. Organic Letters, 20, 3061-3064. [Google Scholar] [CrossRef
[19] Huy, P.H. (2019) Formamide Catalysis Facilitates the Transformation of Aldehydes into Geminal Dichlorides. Synthesis, 51, 2474-2483. [Google Scholar] [CrossRef
[20] Wang, L., Zhang, T., Sun, W., He, Z., Xia, C., Lan, Y., et al. (2017) C-O Functionalization of α-Oxyboronates: A Deoxygenative gem-Diborylation and gem-Silylborylation of Aldehydes and Ketones. Journal of the American Chemical Society, 139, 5257-5264. [Google Scholar] [CrossRef
[21] He, Z., Hu, Y., Xia, C. and Liu, C. (2019) Recent Advances in the Borylative Transformation of Carbonyl and Carboxyl Compounds. Organic & Biomolecular Chemistry, 17, 6099-6113. [Google Scholar] [CrossRef
[22] Li, J., Wang, H., Qiu, Z., Huang, C. and Li, C. (2020) Metal-Free Direct Deoxygenative Borylation of Aldehydes and Ketones. Journal of the American Chemical Society, 142, 13011-13020. [Google Scholar] [CrossRef
[23] Singh, D.K., Prasad, S.S., Kim, J. and Kim, I. (2019) One-Pot, Three-Component Approach to Diarylacetonitriles. Organic Chemistry Frontiers, 6, 669-673. [Google Scholar] [CrossRef
[24] Prasad, S.S., Joshi, D.R. and Kim, I. (2021) BF3·OEt2-Catalyzed One-Pot Three-Component Access to Diarylmethylazides. Tetrahedron Letters, 67, 152820-152824. [Google Scholar] [CrossRef
[25] Prasad, S.S., Singh, D.K. and Kim, I. (2019) One-Pot, Three-Component Approach to Diarylmethylphosphonates: A Direct Entry to Polycyclic Aromatic Systems. The Journal of Organic Chemistry, 84, 6323-6336. [Google Scholar] [CrossRef
[26] Prasad, S.S., Joshi, D.R. and Kim, I. (2021) Facile Access to 3,4-Disubstituted 2H-Chromenes via Domino [4+2] Annulation. Synthesis, 53, 1503-1512. [Google Scholar] [CrossRef
[27] Asako, S., Ishihara, S., Hirata, K. and Takai, K. (2019) Deoxygenative Insertion of Carbonyl Carbon into a C(sp3)-H Bond: Synthesis of Indolines and Indoles. Journal of the American Chemical Society, 141, 9832-9836. [Google Scholar] [CrossRef
[28] Luo, J., Yao, J., Wang, D., Dong, Y., et al. (2021) Molybdenum-Catalyzed Deoxygenative Cyclopropanation of 1,2‐dicarbonyl or Monocarbonyl Compounds. Angewandte Chemie International Edition, 60, 15254-15259. [Google Scholar] [CrossRef
[29] Cheng, B., Srsen, M. and Konig, B. (2020) Umpolung Difunctionalization of Carbonyls via Visible-Light Photoredox Catalytic Radical-Carbanion Relay. Journal of the American Chemical Society, 142, 7524-7531. [Google Scholar] [CrossRef
[30] Wang, H., Dai, X. and Li, C. (2017) Aldehydes as Alkyl Carbanion Equivalents for Additions to Carbonyl Compounds. Nature Chemistry, 9, 374-378. [Google Scholar] [CrossRef
[31] Song, H., Liu, Y. and Wang, Q. (2019) Ketones and Aldehydes as Alkyl Radical Equivalents for C-H Functionalization of Heteroarenes. Science Advances, 5, eaax9955. [Google Scholar] [CrossRef
[32] Wang, Z., Liu, Q., Ji, X., Deng, G. and Huang, H. (2020) Bromide-Promoted Visible-Light-Induced Reductive Minisci Reaction with Aldehydes. ACS Catalysis, 10, 154-159. [Google Scholar] [CrossRef
[33] Byrne, P.A. and Gilheany, D.G. (2013) Gilheany, The Modern Interpretation of the Wittig Reaction Mechanism. Chemical Society Reviews, 42, 6670-6696.
[34] Swamy, K.C.K., Kumar, N.N.B., Balaraman, E. and Kumar, K.V.P.P. (2009) Mitsunobu and Related Reactions: Advances and Applications. Chemical Reviews, 109, 2551-2651. [Google Scholar] [CrossRef
[35] Qu, J.P. (2024) Visible-Light-Mediated Deoxygenative Transformation of 1,2-Dicarbonyl Compounds through Energy Transfer Process. Nature Communications, 15, Article No. 9240.
[36] Suzuki, R., Taiga, A., Deufel, F., et al. (2024) Photocatalytic Carbyne Reactivity of Phosphorus Ylides for Three-Component Formal Cycloaddition Reactions. Nature Synthesis, 3, 1385-1391.
[37] Taiga, A., Daisuke, Y., Kohsuke, O. and Takashi, O. (2025) Deoxygenative [3+2] Annulation of α, β-Unsaturated Carbonyl Compounds and Electron-Rich Olefins via Photocatalytic Umpolung of Triarylphosphine. Journal of the American Chemical Society, 147, 24220-24224.
[38] Qiu, J., Zhang, X., Zheng, H. and Zhu, G. (2025) Photocatalytic Phosphine-Mediated Deoxygenative [3+2] Cycloaddition of α, β-Unsaturated Carbonyls and Alkenes. Journal of the American Chemical Society, 147, 19004-19012. [Google Scholar] [CrossRef