Synthesis, Table of Contents Synthesis 2022; 54(04): 1108-1114DOI: 10.1055/a-1653-2685 feature SN2′ Defluorinative Allylation of Trifluoromethylalkenes with Allylsilanes Authors Meng-Meng Sun Haidong Liu Chuan Zhu ∗ Chao Feng ∗ Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract An SN2′ defluorinative allylation of trifluoromethylalkenes with readily available allylsilanes to access homoallyl gem-difluoroalkenes is reported. The reaction is triggered by a catalytic amount of TBAF, with the extruded fluoride in the reaction serving as a sustainable activator for organosilanes. The high efficiency, good functional group tolerance, and mild reaction conditions underline the potential of this method in synthetic chemistry. Key words Key words gem-difluoroalkene - trifluoromethylalkene - allylsilane - C–F bond cleavage - allylation Full Text References References For selected examples, see: 1a Lim MH, Kim HO, Moon HR, Chun MW, Jeong LS. Org. Lett. 2002; 4: 529 1b Pan Y, Qiu J, Silverman RB. J. Med. Chem. 2003; 46: 5292 1c Fujii K, Nakamoto Y, Hatano K, Kanetsuki Y. JP Patent 2006016331 A, 2006 For selected examples, see: 2a Ma Q, Wang Y, Tsui GC. Angew. Chem. Int. Ed. 2020; 59: 11293 2b Lu X, Wang Y, Zhang B, Pi J.-J, Wang X.-W, Gong T.-J, Xiao B, Fu Y. J. Am. Chem. Soc. 2017; 139: 12632 2c Sakaguchi H, Uetake Y, Ohashi M, Niwa T, Ogoshi S, Hosoya T. J. Am. Chem. Soc. 2017; 139: 12855 3a Yuan K, Feoktistova T, Cheong PH.-Y, Altman RA. Chem. Sci. 2021; 12: 1363 3b Liu C, Zhu C, Cai Y, Jiang H. Angew. Chem. Int. Ed. 2021; 60: 12038 3c Zubkov MO, Kosobokov MD, Levin VV, Kokorekin VA, Korlyukov AA, Hu J, Dilman AD. Chem. Sci. 2020; 11: 737 3d Zhu C, Song S, Zhou L, Wang D.-X, Feng C, Loh T.-P. Chem. Commun. 2017; 53: 9482 For a review, see: 4a Liu C, Zeng H, Zhu C, Jiang H. Chem. Commun. 2020; 56: 10442 For recent examples, see: 4b Lin TY, Pan Z, Tu Y, Zhu S, Wu H.-H, Liu Y, Li Z, Zhang J. Angew. Chem. Int. Ed. 2020; 59: 22957 4c Liu C, Zhu C, Cai Y, Yang Z, Zeng H, Chen F, Jiang H. Chem. Eur. J. 2020; 26: 1953 5 Fuqua SA, Duncan WG, Silverstein RM. Tetrahedron Lett. 1964; 1461 For a review, see: 6a Zhang X, Cao S. Tetrahedron Lett. 2017; 58: 375 For recent examples, see: 6b Wang S, Cheng B.-Y, Sršen M, König H. J. Am. Chem. Soc. 2020; 142: 7524 7 Fujita T, Fuchibe K, Ichikawa J. Angew. Chem. Int. Ed. 2019; 58: 390 8a Bégué J.-P, Bonnet-Delpon D, Rock MH. Tetrahedron Lett. 1995; 36: 5003 8b Fuchikami T, Shibata Y, Suzuki Y. Tetrahedron Lett. 1986; 27: 3173 9a Jang YJ, Rose D, Mirabi B, Lautens M. Angew. Chem. Int. Ed. 2018; 57: 16147 9b Zhang C, Lin Z, Zhu Y, Wang C. J. Am. Chem. Soc. 2021; 143: 11602 9c Lan Y, Yang F, Wang C. ACS Catal. 2018; 8: 9245 9d Lin Z, Lan Y, Wang C. ACS Catal. 2019; 9: 775 9e Lu X, Wang X.-X, Gong T.-J, Pi J.-J, He S.-J, Fu Y. Chem. Sci. 2019; 10: 809 9f Kojima R, Akiyama S, Ito H. Angew. Chem. Int. Ed. 2018; 57: 7196 9g Gao P, Yuan C, Zhao Y, Shi Z. Chem 2018; 4: 2201 10a Lang SB, Wiles RJ, Kelly CB, Molander GA. Angew. Chem. Int. Ed. 2017; 56: 15073 10b Yue W.-J, Day CS, Martin R. J. Am. Chem. Soc. 2021; 143: 6395 10c Xia P.-J, Song D, Ye Z.-P, Hu Y.-Z, Xiao J.-A, Xiang H.-Y, Chen X.-Q, Yang H. Angew. Chem. Int. Ed. 2020; 59: 6706 10d Xu W, Jiang H, Leng J, Ong HW, Wu J. Angew. Chem. Int. Ed. 2020; 59: 4009 10e Guo Y.-Q, Wang R, Song H, Liu Y, Wang Q. Org. Lett. 2020; 22: 709 11 Gao X.-T, Zhang Z, Wang X, Tian J.-S, Xie S.-L, Zhou F, Zhou J. Chem. Sci. 2020; 11: 10414 12a Bao W, Kossen H, Schneider U. J. Am. Chem. Soc. 2017; 139: 4362 12b García-Ruiz C, Chen JL.-Y, Sandford C, Feeney K, Lorenzo P, Berionni G, Mayr H, Aggarwal VK. J. Am. Chem. Soc. 2017; 139: 15324 12c Luo C, Bandar JS. J. Am. Chem. Soc. 2019; 141: 14120 12d Mizuno K, Ikeda M, Otsuji Y. Tetrahedron Lett. 1985; 26: 461 13 Zhu C, Sun M.-M, Chen K, Feng C. Angew. Chem. Int. Ed. 2021; 60: 20237 14a Tian P, Feng C, Loh T.-P. Nat. Commun. 2015; 6: 7472 14b Zhou L, Zhu C, Bi P, Feng C. Chem. Sci. 2019; 10: 1114 14c Zhu C, Zhang Y.-F, Liu Z.-Y, Zhou L, Liu H, Feng C. Chem. Sci. 2019; 10: 6721 14d Tang L, Liu Z.-Y, She W, Feng C. Chem. Sci. 2019; 10: 8701 14e Zhu C, Liu Z.-Y, Tang L, Zhang H, Zhang Y.-F, Walsh PJ, Feng C. Nat. Commun. 2020; 11: 4860 15 Kawai M, Onaka M, Izumi Y. Chem. Lett. 1986; 15: 381 Supplementary Material Supplementary Material Supporting Information (PDF) (opens in new window)
