自由基介导的未活化烯烃的官能团向远端迁移反应研究进展
Recent Progress of Radical-Mediated Difunctionalization of Unactivated Alkenes through Distal Migration of Functional Groups
DOI: 10.12677/JOCR.2022.101001, PDF,   
作者: 秦一洲*：浙江师范大学化学与生命科学学院，浙江 金华
关键词: 自由基；未活化烯烃；官能团远程迁移；Radicals； Unactivated Alkenes； Remote Migration of Functional Groups
摘要: 自由基介导的烯烃1,2-双官能化大大拓展了烯烃的应用范围，近年来已成为热门研究领域。通常，烯烃的应用范围主要局限于活化的烯烃。然而，一类用于未活化的烯烃的官能化的通用策略已经开发出来。本文总结了分子内官能团向远端迁移的策略的最新进展，该策略已经有效地应用于自由基介导的未活化烯烃的双官能化，包括芳基，氰基，杂芳基，亚氨基，羰基，炔基和烯基在内的官能团。
Abstract: Radical-mediated 1,2-difunctionalization of alkenes has greatly expanded the application range of alkenes and has become a hot research area in recent years. In general, however, the scope of alkene is largely restricted to the activated alkenes. However, a general strategy for functionalization of unactivated olefins has been developed. This paper summarizes the latest progress in the strategy of distal migration of intramolecular functional groups. This strategy has been effectively applied to the bifunctionalization of non activated olefins mediated by free radicals, including aryl, cyano, heteroaryl, imino, carbonyl, alkynyl and alkenyl functional groups.
文章引用：秦一洲. 自由基介导的未活化烯烃的官能团向远端迁移反应研究进展[J]. 有机化学研究, 2022, 10(1): 1-17. https://doi.org/10.12677/JOCR.2022.101001

参考文献

[1] Pintauer, T. and Matyjaszewski, K. (2008) Atom Transfer Radical Addition and Polymerization Reactions Catalyzed by ppm Amounts of Copper Complexes. Chemical Society Reviews, 37, 1087-1097. [Google Scholar] [CrossRef] [PubMed]
[2] Studer, A. and Bossart, M. (2001) Radical Aryl Migration Reactions. Tetrahedron, 57, 9649-9667. [Google Scholar] [CrossRef] 
[3] Liu, X., Xiong, F., Huang, X., Xu, L., Li, P. and Wu, X. (2013) Copper-Catalyzed Trifluoromethylation-Initiated Radical 1,2-Aryl Migration in α,α-Diaryl Allylic Alcohols. Angewandte Chemie International Edition, 52, 6962-6966. [Google Scholar] [CrossRef] [PubMed]
[4] Palframan, M.J., Tchabanenko, K. and Robertson, J. (2006) Arylpyrrolidinones Via Radical 1,4-Aryl Migration And 5-Endo-Trig Cyclization of N-(2-Bromoallyl)Arylcarboxamides. Tetrahedron Letters, 47, 8423-8425. [Google Scholar] [CrossRef] 
[5] Wu, Z., Ren, R. and Zhu, C. (2016) Combination of a Cyano Migration Strategy and Alkene Difunctionalization: The Elusive Selective Azidocyanation of Unactivated Olefins. Angewandte Chemie International Edition, 55, 10821-10824. [Google Scholar] [CrossRef] [PubMed]
[6] He, Y.T., Li, L.H., Yang, Y.F., et al.(2014) Copper-Catalyzed Intermolecular Cyanotrifluoromethylation of Alkenes. Organic Letters, 16, 270-273. [Google Scholar] [CrossRef] [PubMed]
[7] Leroux, F., Jeschke, P. and Schlosser, M. (2005) α-Fluorinated Ethers, Thioethers, and Amines: Anomerically Biased Species. Chemical Reviews, 105, 827-856. [Google Scholar] [CrossRef] [PubMed]
[8] Ji, M., Wu, Z., Yu, J., Wan, X. and Zhu, C. (2017) Cyanotrifluoromethylthiolation of Unactivated Olefins through Intramolecular Cyano Migration. Advanced Synthesis & Catalysis, 359, 1959-1962. [Google Scholar] [CrossRef] 
[9] Cametti, M., Crousse, B., Metrangolo, P., Milani, R. and Resnati, G. (2012) The Fluorous Effect In Biomolecular Applications. Chemical Society Reviews, 41, 31-42. [Google Scholar] [CrossRef] 
[10] Ren, R., Wu, Z., Huan, L. and Zhu, C. (2017) Synergistic Strategies of Cyano Migration and Photocatalysis for Difunctionalization of Unactivated Alkenes: Synthesis of Di- and Mono-Fluorinated Alkyl Nitriles. Advanced Synthesis & Catalysis, 359, 3052-3056. [Google Scholar] [CrossRef] 
[11] Wang, N., Li, L., Li, Z.L., et al. (2016) Catalytic Diverse Radical-Mediated 1,2-Cyanofunctionalization of Unactivated Alkenes via Synergistic Remote Cyano Migration and Protected Strategies. Organic Letters, 18, 6026-6029. [Google Scholar] [CrossRef] [PubMed]
[12] McGrath, N.A., Brichacek, M. and Njardarson, J.T. (2010) A Graphical Journey of Innovative Organic Architectures That Have Improved Our Lives. Journal of Chemical Education, 87, 1348-1349. [Google Scholar] [CrossRef] 
[13] Wu, Z., Wang, D., Liu, Y., Huan, L. and Zhu, C. (2017) Chemo- and Regioselective Distal Heteroaryl ipso-Migration: A General Protocol for Heteroarylation of Unactivated Alkenes. Journal of the American Chemical Society, 139, 1388-1391. [Google Scholar] [CrossRef] [PubMed]
[14] Yu, J., Wang, D., Xu, Y., Wu, Z. and Zhu, C. (2018) Distal Functional Group Migration for Visible-Light Induced Carbo-Difluoroalkylation/Monofluoroalkylation of Unactivated Alkenes. Advanced Synthesis & Catalysis, 360, 744-750. [Google Scholar] [CrossRef] 
[15] Gu, L., Gao, Y., Ai, X., et al. (2017) Direct Alkylheteroarylation Of Alkenes Via Photoredox Mediated C-H Functionalization. Chemical Communications, 53, 12946-12949. [Google Scholar] [CrossRef] 
[16] Li, Z.L., Li, X.H., Wang, N., Yang, N.Y. and Liu, X.Y. (2016) Radical-Mediated 1,2-Formyl/Carbonyl Functionalization of Alkenes and Application to the Construction of Medium-Sized Rings. Angewandte Chemie International Edition, 55, 15100-15104. [Google Scholar] [CrossRef] [PubMed]
[17] Xu, Y., Wu, Z., Jiang, J., Ke, Z. and Zhu, C. (2017) Merging Distal Alkynyl Migration and Photoredox Catalysis for Radical Trifluoromethylative Alkynylation of Unactivated Olefins. Angewandte Chemie International Edition, 56, 4545-4548. [Google Scholar] [CrossRef] [PubMed]
[18] Tang, X. and Studer, A. (2017) α-Perfluoroalkyl-β-Alkynylation of Alkenes via Radical Alkynyl Migration. Chemical Science, 8, 6888-6892. [Google Scholar] [CrossRef] 
[19] Studer, A. and Curran, D.P. (2014) The Electron Is A Catalyst. Nature Chemistry, 6, 765-773. [Google Scholar] [CrossRef] [PubMed]
[20] Tang, X. and Studer, A. (2018) Alkene 1,2-Difunctionalization by Radical Alkenyl Migration. Angewandte Chemie International Edition, 57, 814-817. [Google Scholar] [CrossRef] [PubMed]

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