炔丙基克莱森重排的研究进展
Research Progress on the Propargyl Claisen Rearrangement
DOI: 10.12677/jocr.2025.134037, PDF,   
作者: 李泽彬：浙江师范大学化学与材料科学学院，浙江 金华
关键词: 联烯；炔丙基乙烯基醚；克莱森重排；Allene； Propargyl Vinyl Ethers； Claisen Rearrangement
摘要: 炔丙基克莱森重排是有机合成领域的经典反应方法，其核心机制是炔丙基乙烯基醚通过[3,3]-σ迁移重排反应，制备官能化联烯。在实践中，若选用结构合适的炔丙基乙烯基醚作为起始原料，并与之匹配精准调控的反应条件，可推动新型多米诺反应方法学的进一步开发。在该类方法学体系中，联烯并非是最终产物，而是作为关键活性中间体，支撑合成多种重要类别有机化合物的高效合成。
Abstract: The propargyl Claisen rearrangement is a well-known type of reaction method in organic synthesis, whose core lies in the preparation of functionalized allenes through the [3,3]-sigmatropic rearrangement of propargyl vinyl ethers. In practice, if structurally appropriate propargyl vinyl ethers are selected as starting materials and combined with matching reaction conditions, it can further promote the development of novel domino reaction methodologies. In such methodological systems, allenes are not the final products but serve as key intermediates to support the synthesis of a wide range of important classes of organic compounds.
文章引用：李泽彬. 炔丙基克莱森重排的研究进展[J]. 有机化学研究, 2025, 13(4): 380-391. https://doi.org/10.12677/jocr.2025.134037

参考文献

[1] Claisen, L. (1912) Über Umlagerung von Phenol‐Allyläthern in C‐Allyl‐Phenole. Berichte der Deutschen Chemischen Gesellschaft, 45, 3157-3166. [Google Scholar] [CrossRef] 
[2] Hu, M.J., Liang, Y.C., Ru, L.Y., Ye, S., Zhang, L., Huang, X., Bao, M., Kong, L.C. and Peng, B. (2023) Defluorinative Multi-Functionalization of Fluoroaryl Sulfoxides Enabled by Fluorine-Assisted Temporary Dearomatization. Angewandte Chemie International Edition, 62, e202306914.
[3] Hiersemann, M. and Abraham, L. (2002) Catalysis of the Claisen Rearrangement of Aliphatic Allyl Vinyl Ethers. European Journal of Organic Chemistry, 2002, 1461-1471.
[4] Castro, A.M.M. (2004) Claisen Rearrangement over the Past Nine Decades. Chemical Reviews, 104, 2939-3002. [Google Scholar] [CrossRef] [PubMed]
[5] Ziegler, F.E. (1988) The Thermal, Aliphatic Claisen Rearrangement. Chemical Reviews, 88, 1423-1452. [Google Scholar] [CrossRef] 
[6] Hiersemann, M. and Nubbemeyer, U. (2007) The Claisen Rearrangement. Wiley-VCH.
[7] Thyagarajan, B.S., Balasubramanian, K.K. and Rao, R.B. (1963) Studies in Claisen Rearrangement-I, 2-Butyn-1,4-Diyl Bis-(aryl Ethers). Tetrahedron Letters, 4, 1393-1398. [Google Scholar] [CrossRef] 
[8] Black, D.K. and Landor, S.R. (1965) 1256. Allenes. Part X. The Claisen-Cope Rearrangement of Propargyl Vinyl Systems. Journal of the Chemical Society, 0, 6784-6788. [Google Scholar] [CrossRef] 
[9] Ma, S. (2005) Some Typical Advances in the Synthetic Applications of Allenes. Chemical Reviews, 105, 2829-2872. [Google Scholar] [CrossRef] [PubMed]
[10] Sherry, B.D. and Toste, F.D. (2004) Gold(I)-Catalyzed Propargyl Claisen Rearrangement. Journal of the American Chemical Society, 126, 15978-15979. [Google Scholar] [CrossRef] [PubMed]
[11] Saucy, G. and Marbet, R. (1967) Über eine neuartige Synthese von β‐Ketoallenen durch Reaktion von tertiären Acetylencarbinolen mit Vinyläthern eine ergiebige methode zur darstellung des Pseudojonons und verwandter verbindungen. Helvetica Chimica Acta, 50, 1158-1167. [Google Scholar] [CrossRef] 
[12] Wang, C., Zhao, W., Li, H. and Guo, L. (2009) Solvent-Free Synthesis of Unsaturated Ketones by the Saucy-Marbet Reaction Using Simple Ammonium Ionic Liquid as a Catalyst. Green Chemistry, 11, 843-847. [Google Scholar] [CrossRef] 
[13] Crandall, J.K. and Tindell, G.L. (1970) A General Synthesis of β-Allenic Esters from Prop-2-Ynyl Alcohols. Journal of the Chemical Society D: Chemical Communications, 0, 1411-1412. [Google Scholar] [CrossRef] 
[14] Nonoshita, K., Banno, H., Maruoka, K. and Yamamoto, H. (1990) Organoaluminum-Promoted Claisen Rearrangement of Allyl Vinyl Ethers. Journal of the American Chemical Society, 112, 316-322. [Google Scholar] [CrossRef] 
[15] Mori, K. (2012) Pheromone Synthesis. Part 249: Syntheses of Methyl (R,E)-2,4,5-Tetradecatrienoate and Methyl (2E,4Z)-2,4-Decadienoate, the Pheromone Components of the Male Dried Bean Beetle, Acanthoscelides obtectus (Say). Tetrahedron, 68, 1936-1946. [Google Scholar] [CrossRef] 
[16] Tejedor, D., García-Tellado, F., Santos-Expósito, A., Méndez-Abt, G. and Ruiz-Pérez, C. (2009) Trialkylamine versus Trialkylphosphine: Catalytic Conjugate Addition of Alcohols to Alkyl Propiolates. Synlett, 2009, 1223-1226. [Google Scholar] [CrossRef] 
[17] Inanaga, J., Baba, Y. and Hanamoto, T. (1993) Organic Synthesis with Trialkylphosphine Catalysts. Conjugate Addition of Alcohols to Α,β-Unsaturated Alkynic Acid Esters. Chemistry Letters, 22, 241-244. [Google Scholar] [CrossRef] 
[18] Inuki, S., Oishi, S., Fujii, N. and Ohno, H. (2008) Total Synthesis of (±)-Lysergic Acid, Lysergol, and Isolysergol by Palladium-Catalyzed Domino Cyclization of Amino Allenes Bearing a Bromoindolyl Group. Organic Letters, 10, 5239-5242. [Google Scholar] [CrossRef] [PubMed]
[19] de Armas, P., García-Tellado, F., Marrero-Tellado, J.J., Tejedor, D., Maestro, M.A. and Gonzalez-Platas, J. (2001) Alkynoates as a Source of Reactive Alkylinides for Aldehyde Addition Reactions. Organic Letters, 3, 1905-1908. [Google Scholar] [CrossRef] [PubMed]
[20] Kurtz, K.C.M., Frederick, M.O., Lambeth, R.H., Mulder, J.A., Tracey, M.R. and Hsung, R.P. (2006) Synthesis of Chiral Allenes from Ynamides through a Highly Stereoselective Saucy-Marbet Rearrangement. Tetrahedron, 62, 3928-3938. [Google Scholar] [CrossRef] 
[21] Armendariz-Gonzalez, E., Saputra, A., Mureka, E.W., Locicero, C.M., Womble, G.L., Tan, G., et al. (2025) Cascade Grignard Addition: Propargyl Claisen Rearrangement for the Stereoselective Synthesis of α-Allene Quaternary Centers in Cyclohexanones. Organic Letters, 27, 7767-7772. [Google Scholar] [CrossRef] [PubMed]
[22] Shi, C.-Y., Li, L., Kang, W., Zheng, Y.-X. and Ye, L.-W. (2021) Claisen Rearrangement Triggered by Transition Metal-Catalyzed Alkyne Alkoxylation. Coordination Chemistry Reviews, 446, Article ID: 214131. [Google Scholar] [CrossRef] 
[23] Sherry, B.D., Maus, L., Laforteza, B.N. and Toste, F.D. (2006) Gold(I)-Catalyzed Synthesis of Dihydropyrans. Journal of the American Chemical Society, 128, 8132-8133. [Google Scholar] [CrossRef] [PubMed]
[24] Wang, Q., Aparaj, S., Akhmedov, N.G., Petersen, J.L. and Shi, X. (2012) Ambient Schmittel Cyclization Promoted by Chemoselective Triazole-Gold Catalyst. Organic Letters, 14, 1334-1337. [Google Scholar] [CrossRef] [PubMed]
[25] Garayalde, D., Gómez-Bengoa, E., Huang, X., Goeke, A. and Nevado, C. (2010) Mechanistic Insights in Gold-Stabilized Nonclassical Carbocations: Gold-Catalyzed Rearrangement of 3-Cyclopropyl Propargylic Acetates. Journal of the American Chemical Society, 132, 4720-4730. [Google Scholar] [CrossRef] [PubMed]
[26] Wang, Y.-P., Zhang, X.-P., Xie, M.-S. and Guo, H.-M. (2023) Cobalt(II)-Catalyzed Enantioselective Propargyl Claisen Rearrangement: Access to Allenyl-Substituted Quaternary β-Ketoesters. Organic Letters, 25, 7105-7109. [Google Scholar] [CrossRef] [PubMed]
[27] Massad, I. and Marek, I. (2025) Iterative Synthesis of Stereodefined Polyacetals and Their Domino-Coates-Claisen Rearrangement. Chemical Science, 16, 3946-3952. [Google Scholar] [CrossRef] [PubMed]
[28] Liu, Y.-B., Hu, H.-P., Zheng, H.-F., Xia, Y., Liu, X.-H., Lin, L.-L. and Feng, X.-M. (2014) Nickel(II)‐Catalyzed Asymmetric Propargyl and Allyl Claisen Rearrangements to Allenyl‐ and Allyl‐Substituted β‐Ketoesters. Angewandte Chemie International Edition, 53, 11579-11582. [Google Scholar] [CrossRef] [PubMed]
[29] Gao, H., Xiao, T. and Jiang, Y. (2024) Oxy-Difluoroallylation of Ynamides by Nickel-Catalyzed Tandem Alkoxylation/Claisen Rearrangement. Organic Letters, 26, 8832-8836. [Google Scholar] [CrossRef] [PubMed]
[30] Tejedor, D., Méndez‐Abt, G. and García‐Tellado, F. (2009) A Convenient Domino Access to Substituted Alkyl 1,2‐Dihydropyridine‐3‐Carboxylates from Propargyl Enol Ethers and Primary Amines. Chemistry—A European Journal, 16, 428-431. [Google Scholar] [CrossRef] [PubMed]
[31] Tejedor, D., Méndez‐Abt, G. and García‐Tellado, F. (2010) Microwave‐Assisted Diversity‐Oriented Domino Synthesis of Functionalized Nicotinic Acid Derivatives. European Journal of Organic Chemistry, 2010, 6582-6587. [Google Scholar] [CrossRef] 
[32] Tejedor, D., Méndez‐Abt, G., Cotos, L. and García‐Tellado, F. (2012) Merging Domino and Redox Chemistry: Stereoselective Access to Di‐ and Trisubstituted β,γ‐Unsaturated Acids and Esters. Chemistry—A European Journal, 18, 3468-3472. [Google Scholar] [CrossRef] [PubMed]
[33] Tejedor, D., Méndez‐Abt, G., Cotos, L., Ramirez, M.A. and García‐Tellado, F. (2011) A Microwave‐Assisted Domino Rearrangement of Propargyl Vinyl Ethers to Multifunctionalized Aromatic Platforms. Chemistry—A European Journal, 17, 3318-3321. [Google Scholar] [CrossRef] [PubMed]

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