A Practical Synthesis and Applications of (E)-Diphenyl-β-(trifluoromethyl)vinylsulfonium Triflate

Abstract

(E)-Diphenyl-β-(trifluoromethyl)vinylsulfonium triflate, readily prepared from 2-bromo-3,3,3-trifluoroprop-1-ene in two steps, undergoes double alkylation with active methylene compounds in dimethyl sulfoxide or ethyl acetate, in an open vessel at room temperature, to provide the corresponding trifluoromethylated cyclopropane derivatives in excellent yields. The cyclopropane, ethyl 1-cyano-2-(trifluoromethyl)cyclopropanecarboxylate is subjected to a ring-opening reaction followed by cyclization to afford a trifluoromethylated dihydroaminothiophene, which on oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone furnishes the corresponding trifluoromethylated aminothiophene in a high 88% yield.

Key words

vinylsulfonium salts - heterocycles - cyclization - fluorine - ylides

• References

• 1a An J, Chang N.-J, Song L.-D, Jin Y.-Q, Ma Y, Chen J.-R, Xiao W.-J. Chem. Commun. 2011; 47: 1869
• 1b Xie C, Han D, Hu Y, Liu J, Xie T. Tetrahedron Lett. 2010; 51: 5238
• 1c Yamanaka H, Matsuo J.-i, Kawana A, Mukaiyama T. ARKIVOC 2004; (iii): 42
• 1d Matsuo J.-i, Yamanaka H, Kawana A, Mukaiyama T. Chem. Lett. 2003; 392
• 1e Yamanaka H, Mukaiyama T. Chem. Lett. 2003; 1192
• 1f Kim K, Jimenez LS. Tetrahedron: Asymmetry 2001; 12: 999
• 1g Wang Y, Zhang W, Colandrea VJ, Jimenez LS. Tetrahedron 1999; 55: 10659
• 2a Yar M, Fritz SP, Gates PJ, McGarrile EM, Aggarwal VK. Eur. J. Org. Chem. 2012; 160
• 2b Yar M, Unthank MG, McGarrile EM, Aggarwal VK. Chem.–Asian J. 2011; 6: 372
• 2c Kokotos CG, McGarrigle EM, Aggarwal VK. Synlett 2008; 2191
• 2d Yar M, McGarrigle EM, Aggarwal VK. Angew. Chem. Int. Ed. 2008; 47: 3784
• 2e Unthank MG, Hussain N, Aggarwal VK. Angew. Chem. Int. Ed. 2006; 45: 7066
• 3a Fluorine in Medicinal Chemistry and Chemical Biology. Ojima I. Wiley–Blackwell; Chichester: 2009
• 3b Bégué J.-P, Bonnet-Delpon D. Bioorganic and Medicinal Chemistry of Fluorine . John Wiley & Sons; Hoboken: 2008
• 3c Uneyama K. Organofluorine Chemistry . Blackwell; Oxford: 2006
• 3d Chambers RD. Fluorine in Organic Chemistry . Blackwell; Oxford: 2004
• 3e Hiyama T. Organofluorine Compounds . Springer; New York: 2000
• 3f Hudlicky M, Pavlath AE. Chemistry of Organic Fluorine Compounds II, ACS Monograph 187. American Chemical Society; Washington DC: 1995
• 4a Maeda R, Ishibashi R, Kamaishi R, Hirotaki K, Furuno H, Hanamoto T. Org. Lett. 2011; 13: 6240
• 4b Hirotaki K, Hanamoto T. J. Org. Chem. 2011; 76: 8564
• 4c Maeda R, Ooyama K, Anno R, Shiosaki M, Azema T, Hanamoto T. Org. Lett. 2010; 12: 2548
• 4d Shiosaki M, Unno M, Hanamoto T. J. Org. Chem. 2010; 75: 8326
• 4e Hanamoto T, Yamada K. J. Org. Chem. 2009; 74: 7559
• 4f Hanamoto T, Anno R, Yamada K, Ryu K, Maeda R, Aoi K, Furuno H. Tetrahedron 2009; 65: 2757
• 4g Hanamoto T, Hashimoto E, Miura M, Furuno H, Inanaga J. J. Org. Chem. 2008; 73: 4736
• 5 During the course of our investigation, Lu and co-workers independently reported another preparation and reactions of two types of trifluoromethylated vinylsulfonium salt, see: Lin H, Shen Q, Lu L. J. Org. Chem. 2011; 76: 7359
• 6a Risse J, Fernández-Zúmel MA, Cudré Y, Severin K. Org. Lett. 2012; 14: 3060
• 6b Wen L, Zhang H, Lin H, Shen Q, Lu L. J. Fluorine Chem. 2012; 133: 171
• 6c Petrov VA, Marshall W. J. Fluorine Chem. 2012; 133: 61
• 6d Grygorenko OO, Artamonov OS, Komarov IV, Mykhailiuk PK. Tetrahedron 2011; 67: 803
• 6e Bezdudny AV, Klukovsky D, Simurova N, Mykhailiuk PK, Shishkin OV, Pustovit YM. Synthesis 2011; 119
• 6f Morandi B, Cheang J, Carreira EM. Org. Lett. 2011; 13: 3080
• 6g Morandi B, Mariampillai B, Carreira EM. Angew. Chem. Int. Ed. 2011; 50: 1101
• 6h Morandi B, Carreira EM. Angew. Chem. Int. Ed. 2010; 49: 4294
• 6i Morandi B, Carreira EM. Angew. Chem. Int. Ed. 2010; 49: 938
• 6j Duncton MA. J, Ayala L, Kaub C, Janagani S, Edwards WT, Orike N, Ramamoorthy K, Kincaid J, Kelly MG. Tetrahedron Lett. 2010; 51: 1009
• 6k Mykhailiuk PK, Afonin S, Ulrich AS, Komarov IV. Synthesis 2008; 1757
• 6l Mykhailiuk PK, Afonin S, Palamarchuk GV, Shishkin OV, Ulrich AS, Komarov IV. Angew. Chem. Int. Ed. 2008; 47: 5765
• 6m Wan W, Gao Y, Jiang H, Hao J. J. Fluorine Chem. 2008; 129: 510
• 6n Denton JR, Sukumaran D, Davies HM. L. Org. Lett. 2007; 9: 2625
• 6o Titanyuk ID, Beletskaya IP, Peregudov AS, Osipov SN. J. Fluorine Chem. 2007; 128: 723
• 6p Wang Y, Zhao X, Li Y, Lu L. Tetrahedron Lett. 2004; 45: 7775
• 6q Ghanem A, Lacrampe F, Aboul-Enein HY, Schurig V. Monatsh. Chem. 2005; 136: 1205
• 6r Jiang B, Zhang F, Xiong W. Chem. Commun. 2003; 536
• 6s Katagiri T, Yamaji S, Handa M, Irie M, Uneyama K. Chem. Commun. 2001; 2054
• 6t Katagiri T, Irie M, Uneyama K. Org. Lett. 2000; 2: 2423
• 6u Katagiri T, Irie M, Uneyama K. Tetrahedron: Asymmetry 1999; 10: 2583
• 6v Huisgen R, Mloston G. Tetrahedron Lett. 1989; 30: 7041
• 6w O’Bannon PE. O, Dailey WP. Tetrahedron Lett. 1989; 30: 4197
• 7 Gopinath P, Chandrasekaran S. J. Org. Chem. 2011; 76: 700
• 8a Bowers S, Truong AP, Neitz RJ, Neitzel M, Probst GD, Hom RK, Peterson B, Galemmo Jr RA, Konradi AW, Sham HL, Tóth G, Pan H, Yao N, Artis DR, Brigham EF, Quinn KP, Sauer J, Powell K, Ruslim L, Ren Z, Bard F, Yednock TA, Griswold-Prenner I. Bioorg. Med. Chem. Lett. 2011; 21: 1838
• 8b Bi F, Didiuk MT, Guzman-Perez A, Griffith DA, Liu KK, Walker DP, Zawistoski MP. PCT Patent WO 2009001214, 2008
• 9a Hu C, Hong F, Jiang B, Xu Y. J. Fluorine Chem. 1994; 66: 215
• 9b Taguchi T, Tomizawa G, Kawara A, Nakajima M, Kobayashi Y. J. Fluorine Chem. 1988; 40: 171
• 9c Taguchi T, Tomizawa G, Nakajima M, Kobayashi Y. Chem. Pharm. Bull. 1985; 33: 4077
• 10 Burla MC, Camalli M, Carrozzini B, Cascarano GL, Giacovazzo C, Polidori G, Spagna R. J. Appl. Cryst. 2003; 36: 1103
• 11 Sheldrick GM. SHELXL-97, Program for the Refinement of Crystal Structures. University of Göttingen; Germany: 1997