二碘化钐催化有机反应的研究进展
Research Progress on Samarium Diiodide-Catalyzed Organic Reactions
DOI: 10.12677/jocr.2026.141014, PDF,   
作者: 贾 荣：浙江师范大学化学与材料科学学院，浙江 金华
关键词: 二碘化钐；单电子转移；催化循环；还原偶联；Samarium Diiodide； Single-Electron Transfer； Catalytic Cycle； Reductive Coupling
摘要: 二碘化钐(SmI2)作为一种独特的单电子转移(SET)还原剂，自1977年被Kagan课题组首次系统报道以来，已成为有机合成中构建复杂分子骨架的核心工具。传统SmI2反应依赖化学计量比试剂，存在原子经济性低、废弃物排放多等局限。近年来，催化量SmI2体系的开发突破了Sm3+产物络合物难以解离的关键瓶颈，通过还原剂再生、电子循环、光化学驱动等策略实现了催化剂的高效循环。本文系统综述了SmI2催化反应的核心机制：使用化学计量比的牺牲金属还原剂、通过反向电子转移(BET)将电子循环回收钐，以及光化学再生的最新进展。
Abstract: Samarium diiodide (SmI2), as a unique single-electron transfer (SET) reductant, has become a central tool in constructing complex molecular frameworks in organic synthesis since it was first systematically reported by Kagan’s group in 1977. Traditional SmI2 reactions rely on stoichiometric amounts of reagents, which have limitations such as low atom economy and high waste generation. In recent years, the development of catalytic SmI2 systems has overcome the key bottleneck of difficult dissociation of Sm3+-product complexes, achieving efficient catalyst turnover through reductant regeneration, electron cycling, as well as electrochemical and photochemical driving strategies. This review systematically summarizes the core mechanisms of SmI2-catalyzed reactions: the use of stoichiometric sacrificial metal reductants, electron cycling back to Sm through back electron transfer (BET), and the latest advances in photochemical regeneration.
文章引用：贾荣. 二碘化钐催化有机反应的研究进展[J]. 有机化学研究, 2026, 14(1): 152-163. https://doi.org/10.12677/jocr.2026.141014

参考文献

[1] Girard, P., Namy, J.L. and Kagan, H.B. (1980) Divalent Lanthanide Derivatives in Organic Synthesis. 1. Mild Preparation of Samarium Iodide and Ytterbium Iodide and Their Use as Reducing or Coupling Agents. Journal of the American Chemical Society, 102, 2693-2698. [Google Scholar] [CrossRef] 
[2] Namy, J.L., Girard, P., Kagan, H.B. (1977) Divalent Lanthanide Derivatives in Organic Synthesis. I. Mild Preparation of Samarium Diiodide and Ytterbium Diiodide and Their Use as Reducing or Coupling Agents. Nouveau Journal de Chimie, 1, 5-7.
[3] Nicolaou, K.C., Ellery, S.P. and Chen, J.S. (2009) Samarium Diiodide Mediated Reactions in Total Synthesis. Angewandte Chemie International Edition, 48, 7140-7165. [Google Scholar] [CrossRef] [PubMed]
[4] Gao, Y. and Ma, D. (2022) Samarium Iodide-Mediated C-C Bond Formation in the Total Synthesis of Natural Products. Nature Synthesis, 1, 275-288. [Google Scholar] [CrossRef] 
[5] Conticello, V.P., Gin, D.L. and Grubbs, R.H. (1992) Ring-Opening Metathesis Polymerization of Substituted Bicyclo[2.2.2]Octadienes: A New Precursor Route to Poly(1,4-Phenylenevinylene). Journal of the American Chemical Society, 114, 9708-9710. [Google Scholar] [CrossRef] 
[6] Ashida, Y., Arashiba, K., Nakajima, K. and Nishibayashi, Y. (2019) Molybdenum-Catalysed Ammonia Production with Samarium Diiodide and Alcohols or Water. Nature, 568, 536-540. [Google Scholar] [CrossRef] [PubMed]
[7] Szostak, M., Fazakerley, N.J., Parmar, D. and Procter, D.J. (2014) Cross-Coupling Reactions Using Samarium(II) Iodide. Chemical Reviews, 114, 5959-6039. [Google Scholar] [CrossRef] [PubMed]
[8] Procter, D.J., Flowers, R.A. and Skrydstrup, T. (2009) Organic Synthesis Using Samarium Diiodide: A Practical Guide. The Royal Society of Chemistry.
[9] Corey, E.J. and Zheng, G.Z. (1997) Catalytic Reactions of Samarium (II) Iodide. Tetrahedron Letters, 38, 2045-2048. [Google Scholar] [CrossRef] 
[10] Hélion, F. and Namy, J. (1999) Mischmetall: An Efficient and Low Cost Coreductant for Catalytic Reactions of Samarium Diiodide. The Journal of Organic Chemistry, 64, 2944-2946. [Google Scholar] [CrossRef] [PubMed]
[11] Aspinall, H.C., Greeves, N. and Valla, C. (2005) Samarium Diiodide-Catalyzed Diastereoselective Pinacol Couplings. Organic Letters, 7, 1919-1922. [Google Scholar] [CrossRef] [PubMed]
[12] Ueda, T., Kanomata, N. and Machida, H. (2005) Synthesis of Planar-Chiral Paracyclophanes via Samarium(II)-Catalyzed Intramolecular Pinacol Coupling. Organic Letters, 7, 2365-2368. [Google Scholar] [CrossRef] [PubMed]
[13] Maity, S. and Flowers, R.A. (2019) Synthesis of Planar-Chiral Paracyclophanes via Samarium(II)-Catalyzed Intramolecular Pinacol Coupling. Journal of the American Chemical Society, 141, 3207-3216. [Google Scholar] [CrossRef] [PubMed]
[14] Boyd, E.A., Shin, C., Charboneau, D.J., Peters, J.C. and Reisman, S.E. (2024) Reductive Samarium (Electro)Catalysis Enabled by SmIII-Alkoxide Protonolysis. Science, 385, 847-853. [Google Scholar] [CrossRef] [PubMed]
[15] Huang, H., Garduño-Castro, M.H., Morrill, C. and Procter, D.J. (2019) Catalytic Cascade Reactions by Radical Relay. Chemical Society Reviews, 48, 4626-4638. [Google Scholar] [CrossRef] [PubMed]
[16] Huang, H., McDouall, J.J.W. and Procter, D.J. (2019) SmI2-Catalysed Cyclization Cascades by Radical Relay. Nature Catalysis, 2, 211-218. [Google Scholar] [CrossRef] 
[17] Agasti, S., Beattie, N.A., McDouall, J.J.W. and Procter, D.J. (2021) SmI2-Catalyzed Intermolecular Coupling of Cyclopropyl Ketones and Alkynes: A Link between Ketone Conformation and Reactivity. Journal of the American Chemical Society, 143, 3655-3661. [Google Scholar] [CrossRef] [PubMed]
[18] Mansell, J.I., Yu, S., Li, M., Pye, E., Yin, C., Beltran, F., et al. (2024) Alkyl Cyclopropyl Ketones in Catalytic Formal [3 + 2] Cycloadditions: The Role of SmI2 Catalyst Stabilization. Journal of the American Chemical Society, 146, 12799-12807. [Google Scholar] [CrossRef] [PubMed]
[19] Mini, A., Vyas, H., Gangani, A.J., Melada, M., Shin, A. and Sharma, A. (2025) Merging Ketyl Radical Chemistry and Allylboration via Strain Release: One-Pot Multicomponent Access to Sterically Congested Ketone-Functionalized Organoborons. Organic Letters, 27, 2902-2907. [Google Scholar] [CrossRef] [PubMed]
[20] Novaes, L.F.T., Liu, J., Shen, Y., Lu, L., Meinhardt, J.M. and Lin, S. (2021) Electrocatalysis as an Enabling Technology for Organic Synthesis. Chemical Society Reviews, 50, 7941-8002. [Google Scholar] [CrossRef] [PubMed]
[21] Agasti, S., Beltran, F., Pye, E., Kaltsoyannis, N., Crisenza, G.E.M. and Procter, D.J. (2023) A Catalytic Alkene Insertion Approach to Bicyclo[2.1.1]Hexane Bioisosteres. Nature Chemistry, 15, 535-541. [Google Scholar] [CrossRef] [PubMed]
[22] Roy, D., Mansell, J.I., Barison, G., Yu, S., Katavic, R., Romano, C., et al. (2025) SmI2‐Catalyzed Coupling of Alkyl Housane Ketones and Alkenes in an Approach to Norbornanes. Angewandte Chemie International Edition, 64, e202512018. [Google Scholar] [CrossRef] [PubMed]
[23] Walczak, M.A.A., Krainz, T. and Wipf, P. (2015) Ring-Strain-Enabled Reaction Discovery: New Heterocycles from Bicyclo[1.1.0]Butanes. Accounts of Chemical Research, 48, 1149-1158. [Google Scholar] [CrossRef] [PubMed]
[24] Subbaiah, M.A.M. and Meanwell, N.A. (2021) Bioisosteres of the Phenyl Ring: Recent Strategic Applications in Lead Optimization and Drug Design. Journal of Medicinal Chemistry, 64, 14046-14128. [Google Scholar] [CrossRef] [PubMed]
[25] Chen, R., Bai, Y. and Wei, B. (2025) Samarium Redox Catalysis. Chemical Synthesis, 5, 62. [Google Scholar] [CrossRef] 
[26] Parker, D., Dickins, R.S., Puschmann, H., Crossland, C. and Howard, J.A.K. (2002) Being Excited by Lanthanide Coordination Complexes: Aqua Species, Chirality, Excited-State Chemistry, and Exchange Dynamics. Chemical Reviews, 102, 1977-2010. [Google Scholar] [CrossRef] [PubMed]
[27] Tomar, M., Bhimpuria, R., Kocsi, D., Thapper, A. and Borbas, K.E. (2023) Photocatalytic Generation of Divalent Lanthanide Reducing Agents. Journal of the American Chemical Society, 145, 22555-22562. [Google Scholar] [CrossRef] [PubMed]
[28] Bhimpuria, R., Charaf, R., Ye, K., Thapper, A., Sathyan, H., Ahlquist, M., et al. (2025) A Sm(II)-Based Catalyst for the Reduction of Dinitrogen, Nitrite, and Nitrate to Ammonia or Urea. Chem, 11, Article 102547. [Google Scholar] [CrossRef] 
[29] Kuribara, T., Kaneki, A., Matsuda, Y. and Nemoto, T. (2024) Visible-Light-Antenna Ligand-Enabled Samarium-Catalyzed Reductive Transformations. Journal of the American Chemical Society, 146, 20904-20912. [Google Scholar] [CrossRef] [PubMed]
[30] Tomar, M., Bosch, C., Everaert, J., Bhimpuria, R., Thapper, A., Orthaber, A., et al. (2024) Photocatalyst for Visible-Light-Driven Sm(II)-Mediated Reductions. Organic Letters, 26, 10752-10756. [Google Scholar] [CrossRef] [PubMed]
[31] Johansen, C.M., Boyd, E.A., Tarnopol, D.E. and Peters, J.C. (2024) Photodriven Sm(III)-To-Sm(II) Reduction for Catalytic Applications. Journal of the American Chemical Society, 146, 25456-25461. [Google Scholar] [CrossRef] [PubMed]

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