Ag(I)-Mediated Oxidative Radical Trifluoromethylthiolation of Alkenes

Abstract

A simple, mild, and efficient method for an oxidative radical trifluoromethylthiolation of alkenes through AgSCF₃/K₂S₂O₈ system has been developed. This reaction provides a straightforward way to synthesize a variety of useful α-SCF₃-substituted ketone compounds from a wide range of alkenes in moderate to good yields.

Key words

trifluoromethylthiolation - alkenes - AgSCF₃ - α-SCF₃-substituted ketone - radical pathway

• References and Notes

• 1a Smart BE. J. Fluorine Chem. 2001; 109: 3
• 1b Tlili A, Billard T. Angew. Chem. Int. Ed. 2013; 52: 6818
• 1c Wang H, Vicic DA. Synlett 2013; 24: 1887
• 1d Landelle G, Panossian A, Pazenok S, Vors JP, Leroux FR. Beilstein J. Org. Chem. 2013; 9: 2476
• 1e Xu XH, Matsuzaki K, Shibata N. Chem. Rev. 2015; 115: 731
• 1f Yang X, Wu T, Phipps RJ, Toste FD. Chem. Rev. 2015; 115: 826
• 1g Zhang PP, Lu L, Shen QL. Acta Chim. Sin. 2017; 75: 744 , DOI: 10.6023/A17050202
• 2a Leo A, Hansch C, Elkins D. Chem. Rev. 1971; 71: 525
• 2b Hansch C, Leo A, Taft RW. Chem. Rev. 1991; 91: 165
• 3a Leroux F, Jeschke P, Schlosser M. Chem. Rev. 2005; 105: 827
• 3b Rossi S, Puglisi A, Raimondi L, Benaglia M. ChemCatChem 2018; 10: 2717
• 4a Toulgoat F, Alazet S, Billard T. Eur. J. Org. Chem. 2014; 2415
• 4b Wang J, Sánchez-Roselló M, Aceña JL, Pozo C, Sorochinsky AE, Fustero S, Soloshonok VA, Liu H. Chem. Rev. 2014; 114: 2432
• 4c Tlili A, Toulgoat F, Billard T. Angew. Chem. Int. Ed. 2016; 55: 11726
• 4d Meyer F. Chem. Commun. 2016; 52: 3077
• 4e Anselmi E, Simon C, Marrot J, Bernardelli P, Schio L, Pégot B, Magnier E. Eur. J. Org. Chem. 2017; 6319
• 5a Adams DJ, Clark JH. J. Org. Chem. 2000; 65: 1456
• 5b Teverovskiy G, David S, Surry DS, Buchwald SL. Angew. Chem. Int. Ed. 2011; 50: 7312
• 5c Zhang CP, Vicic DA. J. Am. Chem. Soc. 2011; 134: 183
• 5d Lefebvre Q, Fava E, Nikolaienko P, Rueping M. Chem. Commun. 2014; 50: 6617
• 5e Hu M, Rong J, Miao W, Ni C, Han Y, Hu J. Org. Lett. 2014; 16: 2030
• 5f Chu L, Qing FL. Acc. Chem. Res. 2014; 47: 1513
• 6a Pluta R, Nikolaienko P, Rueping M. Angew. Chem. Int. Ed. 2014; 53: 1650
• 6b Shao X, Xu C, Lu L, Shen QL. Acc. Chem. Res. 2015; 48: 1227
• 6c Chachignon H, Maeno M, Kondo H, Shibata N, Cahard D. Org. Lett. 2016; 18: 2467
• 6d Bu MJ, Lu GP, Cai C. Org. Chem. Front. 2017; 4: 266
• 6e Song HX, Han QY, Zhao CL, Zhang CP. Green Chem. 2018; 20: 1662
• 7a Li Y, Koike T, Akita M. Asian J. Org. Chem. 2017; 6: 445
• 7b Dagousset G, Simon C, Anselmi E, Tuccio B, Billard T, Magnier E. Chem. Eur. J. 2017; 23: 4282
• 7c Yin F, Wang XS. Org. Lett. 2014; 16: 1128
• 8a Guo S, Zhang X, Tang P. Angew. Chem. Int. Ed. 2015; 54: 4065
• 8b Wu H, Xiao Z, Wu J, Guo Y, Xiao JC, Liu C, Chen QY. Angew. Chem. Int. Ed. 2015; 54: 4070
• 8c Wu W, Dai W, Ji X, Cao S. Org. Lett. 2016; 18: 2918
• 8d Chen MT, Tang XY, Shi M. Org. Chem. Front. 2017; 4: 86
• 8e Li M, Petersen JL, Hoover JM. Org. Lett. 2017; 19: 638
• 8f Ji MS, Yu JJ, Zhu C. Chem. Commun. 2018; 54: 6812
• 9a Barata-Vallejo S, Bonesi S, Postigo A. Org. Biomol. Chem. 2016; 14: 7150
• 9b Cheng ZF, Tao TT, Feng YS, Tang WK, Xu JJ, Dai J, Xu HJ. J. Org. Chem. 2018; 83: 499
• 10a Rueping M, Tolstoluzhsky N, Nikolaienko P. Chem. Eur. J. 2013; 19: 14043
• 10b Li SG, Zard SZ. Org. Lett. 2013; 15: 5898
• 10c Huang Y, He X, Lin X, Rong M, Weng Z. Org. Lett. 2014; 16: 3284
• 10d Jiang M, Zhu F, Xiang H, Xu X, Deng L, Yang C. Org. Biomol. Chem. 2015; 13: 6935
• 10e Zheng J, Cheng R, Lin JH, Yu DH, Ma L, Jia L, Liang SH. Angew. Chem. Int. Ed. 2017; 56: 3196
• 11a Bayreuther H, Haas A. Chem. Ber. 1973; 106: 1418
• 11b Kolasa A. J. Fluorine Chem. 1987; 36: 29
• 11c Alazet S, Zimmer L, Billard T. Chem. Eur. J. 2014; 20: 8589
• 11d Glenadel Q, Alazet S, Billard T. J. Fluorine Chem. 2015; 179: 89
• 11e Alazet S, Ismalaj E, Glenadel Q, Bars DL, Billard T. Eur. J. Org. Chem. 2015; 4607
• 11f Shao X. Xu C., Lu L., Shen Q. 2015; 80: 3012
• 11g Wu W, Zhang XX, Liang F, Cao S. Org. Biomol. Chem. 2015; 13: 6992
• 12a Pan S, Huang Y, Qing FL. Chem. Asian J. 2016; 11: 2854
• 12b Pan S, Li H, Huang Y, Xu XH, Qing FL. Org. Lett. 2017; 19: 3247
• 13a Shao X, Wang X, Yang T, Lu L, Shen Q. Angew. Chem. Int. Ed. 2013; 52: 3457
• 13b Bootwicha T, Liu X, Pluta R, Atodiresei I, Rueping M. Angew. Chem. Int. Ed. 2013; 52: 12856
• 13c Wang X, Yang T, Cheng X, Shen Q. Angew. Chem. Int. Ed. 2013; 52: 12860
• 13d Deng QH, Rettenmeier C, Wadepohl H, Gade LH. Chem. Eur. J. 2014; 20: 93
• 13e Vinogradova EV, Müller P, Buchwald SL. Angew. Chem. Int. Ed. 2014; 53: 3125
• 13f Arimori S, Takada M, Shibata N. Org. Lett. 2015; 17: 1063
• 13g Guyon H, Chachignon H, Tognetti V, Joubert L, Cahard D. Eur. J. Org. Chem. 2018; 3756
• 14 Yadav AK, Singh KN. Chem. Commun. 2018; 54: 1976
• 15 Deb A, Manna S, Modak A, Patra T, Maity S, Maiti D. Angew. Chem. Int. Ed. 2013; 52: 9747
• 16a Liu H, Jiang X. Chem. Asian J. 2013; 8: 2546
• 16b Landelle G, Panossian A, Leroux FR. Curr. Top. Med. Chem. 2014; 14: 941
• 16c Rueping M, Liu X, Bootwicha T, Pluta R, Merkens C. Chem. Commun. 2014; 50: 2508
• 17 Yasu Y, Koike T, Akita M. Org. Lett. 2013; 15: 2136
• 18 1-(4-Iodophenyl)-2-[(trifluoromethyl)thio]ethanone (2l) In an oven-dried 25 mL Schlenk tube equipped with a stir bar were added 1-iodo-4-vinylbenzene (1l, 115.0 mg, 0.5 mmol), AgSCF₃ (156.7 mg, 0.75 mmol), and K₂S₂O₈ (270.3 mg, 1.0 mmol). The Schlenk tube was evacuated and refilled with oxygen balloon. DMSO (5 mL) was then added by syringe. The reaction mixture was stirred for 3 h at 35 °C. The crude reaction mixture was purified by column chromatography on silica gel to get product 2l. Light yellow solid, 0.118 g, 68%. ¹H NMR (400 MHz, CDCl₃): δ = 7.93–7.87 (m, 2 H), 7.70–7.64 (m, 2 H), 4.48 (s, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 191.4 (s), 138.4 (s), 133.9 (s), 130.5 (q, J = 306.6 Hz), 129.6 (s), 102.5 (s), 38.0 (q, J = 1.9 Hz). ¹⁹F NMR (376 MHz, CDCl₃): δ = –41.39 (s, 3 F). HRMS (ESI): m/z [M + H]⁺ calcd for C₉H₇F₃IOS: 346.9214; found: 346.9209.
• 19 1-[(Trifluoromethyl)thio]decan-2-one (3b) In an oven-dried 25 mL Schlenk tube equipped with a stir bar were added alkenes 1-decene 1′b (70.1 mg, 0.5 mmol), AgSCF₃ (156.7 mg, 0.75 mmol), and K₂S₂O₈ (270.3 mg, 1.0 mmol). The Schlenk tube was evacuated and refilled with oxygen balloon. DMSO (5 mL) was then added by syringe. The reaction mixture was stirred for 3 h at 35 °C. The crude reaction mixture was purified by column chromatography on silica gel to get product 3b. Light yellow oil, 0.078 g, 61%. ¹H NMR (400 MHz, CDCl₃): δ = 3.83 (s, 2 H), 2.59 (t, J = 7.4 Hz, 2 H), 1.30 (s, 11 H), 0.90 (t, J = 6.9 Hz, 4 H). ¹³C NMR (101 MHz, CDCl₃): δ = 202.9 (s), 130.5 (q, J = 306.5 Hz), 41.2 (s), 40.0 (q, J = 1.8 Hz), 31.8 (s), 29.2 (s), 29.1 (s), 29.0 (s), 23.7 (s), 22.6 (s), 14.0 (s). ¹⁹F NMR (376 MHz, CDCl₃): δ = –41.68 (s, 3 F). HRMS (EI): m/z [M]⁺ calcd for C₁₁H₁₉F₃OS: 256.1109; found: 256.1093
• 20 (8R,9S,13S,14S)-13-Methyl-3-{2-[(trifluoromethyl)thio]acetyl}-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthren-17-one (4a)¹⁷ In an oven-dried 50 mL Schlenk tube equipped with a stir bar were added 3-vinylestrone (140.1 mg, 0.5 mmol), AgSCF₃ (156.7 mg, 0.75 mmol), and K₂S₂O₈ (270.3 mg, 1.0 mmol). The Schlenk tube was evacuated and refilled with oxygen balloon. DMSO (5 mL) was then added by syringe. The reaction mixture was stirred for 3 h at 35 °C. The crude reaction mixture was purified by column chromatography on silica gel to get product 4a. White solid, 0.141 g, 71%. ¹H NMR (400 MHz, CDCl₃): δ = 7.78–7.66 (m, 2 H), 7.44 (d, J = 8.2 Hz, 1 H), 4.51 (s, 2 H), 3.01 (d, J = 5.1 Hz, 2 H), 2.63–2.45 (m, 2 H), 2.38 (td, J = 10.7, 3.8 Hz, 1 H), 2.26–1.99 (m, 4 H), 1.75–1.45 (m, 6 H), 0.95 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 191.8 (s), 146.9 (s), 137.5 (s), 132.4 (s), 130.7 (q, J = 306.4 Hz), 129.0 (s), 126.0 (s), 125.8 (s), 50.6 (s), 47.9 (s), 44.8 (s), 38.3 (q, J = 1.6 Hz), 37.7 (s), 35.8 (s), 31.5 (s), 29.3 (s), 26.2 (s), 25.5 (s), 21.6 (s), 13.8 (s). ¹⁹F NMR (376 MHz, CDCl₃): δ = –41.39 (s, 3 F). HRMS (ESI): m/z [M + H]⁺ calcd for C₂₁H₂₄F₃O₂S: 397.1449; found: 397.1444
• 21 Radical Trapping Experiment Styrene (1a, 10.5 mg, 0.1 mmol), AgSCF₃ (31.3 mg, 0.15 mmol), K₂S₂O₈ (54.1 mg, 0.2 mmol), TEMPO (31.2 mg, 0.2 mmol), and 4,4′-difluorobiphenyl (19.0 mg, 0.1 mmol) were added to a Schlenk tube. The Schlenk tube was evacuated and refilled with oxygen balloon. Then DMSO (1.0 mL) was added by a syringe. The mixture was stirred at 35 °C for 3 h. Trace of the desired product 2a and TEMPO-trifluoromethylthio adduct were detected by ¹⁹F NMR spectroscopy with 4,4′-difluorobiphenyl as the internal standard (δ = –115.78 ppm) based on 1a. The same time, the reaction mixture was analyzed by LC–MS