水作为氧源在有机合成中的研究进展
Recent Advances in the Use of Water as an Oxygen Source in Organic Synthesis
DOI: 10.12677/jocr.2026.142019, PDF,   
作者: 赵嘉轩：兰州交通大学化学化工学院，甘肃 兰州
关键词: 绿色化学；水氧化；有机合成；Green Chemistry； Water Oxidation； Organic Synthesis
摘要: 氧化反应是有机合成中最核心的转化方式之一，但传统化学氧化剂往往伴随着原子利用率低及环境污染等严峻挑战。在“绿色化学”与“原子经济性”理念的驱动下，利用廉价、无毒且储量丰富的水作为氧源直接参与有机转化，已成为现代合成化学的研究热点。然而，水分子的极高热力学稳定性(O-H键能高达118 kJ/mol)使其在温和条件下的活化极具挑战性。本综述系统总结了水作为氧源在有机合成中的最新研究进展与机理探索。
Abstract: Oxidation reactions are among the most fundamental transformations in organic synthesis; however, the use of traditional chemical oxidants often entails severe challenges, including low atom economy and environmental pollution. Driven by the principles of “green chemistry” and “atom economy,” the direct incorporation of water—an inexpensive, non-toxic, and naturally abundant reagent—as an oxygen source in organic transformations has emerged as a highly active frontier in modern synthetic chemistry. Nevertheless, the inherent thermodynamic stability of the water molecule (O-H bond dissociation energy up to 118 kJ/mol) makes its activation under mild conditions exceptionally challenging. This review systematically summarizes recent advances and provides mechanistic insights into the utilization of water as an oxygen source in organic synthesis.
文章引用：赵嘉轩. 水作为氧源在有机合成中的研究进展[J]. 有机化学研究, 2026, 14(2): 203-220. https://doi.org/10.12677/jocr.2026.142019

参考文献

[1] Caron, S., Dugger, R.W., Ruggeri, S.G., Ragan, J.A. and Ripin, D.H.B. (2006) Large-Scale Oxidations in the Pharmaceutical Industry. Chemical Reviews, 106, 2943-2989. [Google Scholar] [CrossRef] [PubMed]
[2] Piera, J. and Bäckvall, J. (2008) Catalytic Oxidation of Organic Substrates by Molecular Oxygen and Hydrogen Peroxide by Multistep Electron Transfer—A Biomimetic Approach. Angewandte Chemie International Edition, 47, 3506-3523. [Google Scholar] [CrossRef] [PubMed]
[3] Targhan, H., Evans, P. and Bahrami, K. (2021) A Review of the Role of Hydrogen Peroxide in Organic Transformations. Journal of Industrial and Engineering Chemistry, 104, 295-332. [Google Scholar] [CrossRef] 
[4] Liu, J., Guðmundsson, A. and Bäckvall, J.E. (2021) Efficient Aerobic Oxidation of Organic Molecules by Multistep Electron Transfer. Angewandte Chemie International Edition, 60, 15686-15704. [Google Scholar] [CrossRef] [PubMed]
[5] Allen, S.E., Walvoord, R.R., Padilla-Salinas, R. and Kozlowski, M.C. (2013) Aerobic Copper-Catalyzed Organic Reactions. Chemical Reviews, 113, 6234-6458. [Google Scholar] [CrossRef] [PubMed]
[6] Shi, Z., Zhang, C., Tang, C. and Jiao, N. (2012) Recent Advances in Transition-Metal Catalyzed Reactions Using Molecular Oxygen as the Oxidant. Chemical Society Reviews, 41, 3381-3430. [Google Scholar] [CrossRef] [PubMed]
[7] Hu, X., Zhang, G., Bu, F. and Lei, A. (2017) Visible-Light-Mediated Anti-Markovnikov Hydration of Olefins. ACS Catalysis, 7, 1432-1437. [Google Scholar] [CrossRef] 
[8] Li, Y., Jiang, X., Zhao, C., Fu, X., Xu, X. and Tang, P. (2017) Silver-Catalyzed Anti-Markovnikov Hydroxyfluorination of Styrenes. ACS Catalysis, 7, 1606-1609. [Google Scholar] [CrossRef] 
[9] Zhang, X., Li, J., Tian, H. and Shi, Y. (2015) Catalytic Asymmetric Bromination of Unfunctionalized Olefins with H2O as a Nucleophile. Chemistry—A European Journal, 21, 11658-11663. [Google Scholar] [CrossRef] [PubMed]
[10] Cao, Y., Lentz, D. and Christmann, M. (2018) Synthesis of Enantioenriched Bromohydrins via Divergent Reactions of Racemic Intermediates from Anchimeric Oxygen Borrowing. Journal of the American Chemical Society, 140, 10677-10681. [Google Scholar] [CrossRef] [PubMed]
[11] Ling, C., Li, H., Li, Y., Zhao, L., Ma, S., Liu, Y., et al. (2025) Homolytic H2O Dissociation into Hydroxyl and Hydrogen Radicals on Sulfur-Deficient Greigite for Efficient Hydration Reactions. Journal of the American Chemical Society, 147, 25052-25060. [Google Scholar] [CrossRef] [PubMed]
[12] Balaraman, E., Khaskin, E., Leitus, G. and Milstein, D. (2013) Catalytic Transformation of Alcohols to Carboxylic Acid Salts and H2 Using Water as the Oxygen Atom Source. Nature Chemistry, 5, 122-125. [Google Scholar] [CrossRef] [PubMed]
[13] Khusnutdinova, J.R., Ben-David, Y. and Milstein, D. (2014) Oxidant-Free Conversion of Cyclic Amines to Lactams and H2 Using Water as the Oxygen Atom Source. Journal of the American Chemical Society, 136, 2998-3001. [Google Scholar] [CrossRef] [PubMed]
[14] Tang, S., Ben-David, Y. and Milstein, D. (2020) Oxidation of Alkenes by Water with H2 Liberation. Journal of the American Chemical Society, 142, 5980-5984. [Google Scholar] [CrossRef] [PubMed]
[15] Kar, S., Zhou, Q., Ben-David, Y. and Milstein, D. (2022) Catalytic Furfural/5-Hydroxymethyl Furfural Oxidation to Furoic Acid/Furan-2,5-Dicarboxylic Acid with H2 Production Using Alkaline Water as the Formal Oxidant. Journal of the American Chemical Society, 144, 1288-1295. [Google Scholar] [CrossRef] [PubMed]
[16] You, C., Lu, L. and Milstein, D. (2025) Catalytic Oxidation of Carbon-Halogen Bonds by Water with H2 Liberation. Journal of the American Chemical Society, 147, 30490-30498. [Google Scholar] [CrossRef] [PubMed]
[17] Liang, Y., Luo, J., You, C., Diskin-Posner, Y. and Milstein, D. (2025) A Hydrogenative Oxidation Strategy for the Single-Step Synthesis of Lactams from N-Heteroarenes Using Water. Nature Catalysis, 8, 98-106. [Google Scholar] [CrossRef] 
[18] Li, G., Morales-Rivera, C.A., Gao, F., Wang, Y., He, G., Liu, P., et al. (2017) A Unified Photoredox-Catalysis Strategy for C(sp3)-H Hydroxylation and Amidation Using Hypervalent Iodine. Chemical Science, 8, 7180-7185. [Google Scholar] [CrossRef] [PubMed]
[19] Yang, X., Ren, B., Guo, H., Liu, R. and Zhou, R. (2024) Metal-and Oxidant-Free Carbonylation of Benzylic and Allylic C-H Bonds with H2O via Dual Oxidative Radical-Polar Crossover. Green Chemistry, 26, 10344-10349. [Google Scholar] [CrossRef] 
[20] Dai, Y., Huang, Y., Wang, Y., Lin, Y., Liu, Y., Wei, Q., et al. (2025) Photocatalytic Asymmetric Oxidation of Phosphines with Water. Journal of the American Chemical Society, 147, 30499-30507. [Google Scholar] [CrossRef] [PubMed]
[21] Ge, R., Wang, Y., Li, Z., Xu, M., Xu, S., Zhou, H., et al. (2022) Selective Electrooxidation of Biomass‐Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel‐Oxide‐Supported Ruthenium Single‐atom Catalyst. Angewandte Chemie International Edition, 61, e202200211. [Google Scholar] [CrossRef] [PubMed]
[22] Liu, M., Feng, T., Wang, Y., Kou, G., Wang, Q., Wang, Q., et al. (2023) Metal-Free Electrochemical Dihydroxylation of Unactivated Alkenes. Nature Communications, 14, Article No. 6467. [Google Scholar] [CrossRef] [PubMed]
[23] Zhang, C., Tang, H., Zhao, X., Shen, X. and Qiu, Y. (2025) Electrochemical Direct Hydroxylation of Benzylic C-H Bonds Assisted by HFIP. Journal of the American Chemical Society, 147, 23297-23307. [Google Scholar] [CrossRef] [PubMed]
[24] Fukuzumi, S., Kishi, T., Kotani, H., Lee, Y. and Nam, W. (2010) Highly Efficient Photocatalytic Oxygenation Reactions Using Water as an Oxygen Source. Nature Chemistry, 3, 38-41. [Google Scholar] [CrossRef] [PubMed]
[25] Li, F., Yu, M., Jiang, Y., Huang, F., Li, Y., Zhang, B., et al. (2011) Chemical and Photochemical Oxidation of Organic Substrates by Ruthenium Aqua Complexes with Water as an Oxygen Source. Chemical Communications, 47, 8949-8951. [Google Scholar] [CrossRef] [PubMed]
[26] Zhang, G., Hu, X., Chiang, C., Yi, H., Pei, P., Singh, A.K., et al. (2016) Anti-Markovnikov Oxidation of β-Alkyl Styrenes with H2O as the Terminal Oxidant. Journal of the American Chemical Society, 138, 12037-12040. [Google Scholar] [CrossRef] [PubMed]
[27] Zheng, Y., Chen, B., Ye, P., Feng, K., Wang, W., Meng, Q., et al. (2016) Photocatalytic Hydrogen-Evolution Cross-Couplings: Benzene C-H Amination and Hydroxylation. Journal of the American Chemical Society, 138, 10080-10083. [Google Scholar] [CrossRef] [PubMed]
[28] Das, A., Nutting, J.E. and Stahl, S.S. (2019) Electrochemical C-H Oxygenation and Alcohol Dehydrogenation Involving Fe-oxo Species Using Water as the Oxygen Source. Chemical Science, 10, 7542-7548. [Google Scholar] [CrossRef] [PubMed]
[29] Jin, K., Maalouf, J.H., Lazouski, N., Corbin, N., Yang, D. and Manthiram, K. (2019) Epoxidation of Cyclooctene Using Water as the Oxygen Atom Source at Manganese Oxide Electrocatalysts. Journal of the American Chemical Society, 141, 6413-6418. [Google Scholar] [CrossRef] [PubMed]
[30] Chung, M., Maalouf, J.H., Adams, J.S., Jiang, C., Román-Leshkov, Y. and Manthiram, K. (2024) Direct Propylene Epoxidation via Water Activation over Pd-Pt Electrocatalysts. Science, 383, 49-55. [Google Scholar] [CrossRef] [PubMed]
[31] Tang, S., Wang, S., Zhang, D., Zhang, X., Yang, G., Wang, Y., et al. (2024) Selective Nickel-Electrocatalyzed Benzylic C-H Oxygenation of Functionalized Alkyl Arenes. Chinese Chemical Letters, 35, Article ID: 108660. [Google Scholar] [CrossRef] 
[32] Wu, H., Wang, Y., Huang, M., Cheng, J., Sa, B., Fang, Y., et al. (2025) Alkene Epoxidation with Water by Confined Active Co Sites on BiVO4 Photoanodes under Visible Light. Angewandte Chemie International Edition, 64, e202420188. [Google Scholar] [CrossRef] [PubMed]
[33] Wang, C., Tong, L., Gu, C., Chen, Z., Sun, J. and Li, J. (2025) Electrophotocatalytic Oxygenation of Unactivated Aliphatic C-H Bonds Using Water as a Sustainable Oxygen Source. Journal of the American Chemical Society, 147, 41539-41548. [Google Scholar] [CrossRef] 
[34] Gao, D., Jin, F., Lee, J.K. and Zare, R.N. (2019) Aqueous Microdroplets Containing Only Ketones or Aldehydes Undergo Dakin and Baeyer-Villiger Reactions. Chemical Science, 10, 10974-10978. [Google Scholar] [CrossRef] [PubMed]
[35] Xue, L., Chen, W., Zheng, P., Geng, J., Zhang, F., Li, X., et al. (2024) Catalyst-Free Oxidation of Styrene to Styrene Oxide Using Circulating Microdroplets in an Oxygen Atmosphere. Journal of the American Chemical Society, 146, 26909-26915. [Google Scholar] [CrossRef] [PubMed]
[36] Meng, Y., Gnanamani, E. and Zare, R.N. (2023) One-Step Formation of Pharmaceuticals Having a Phenylacetic Acid Core Using Water Microdroplets. Journal of the American Chemical Society, 145, 7724-7728. [Google Scholar] [CrossRef] [PubMed]
[37] Bose, S., Mofidfar, M., Zare, R.N. and Gnanamani, E. (2025) Cross-Coupling between Arylboronic Acids and Terminal Alkynes in Water Microdroplets. Journal of the American Chemical Society, 147, 25779-25786. [Google Scholar] [CrossRef] [PubMed]

为你推荐