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Synlett 2019; 30(11): 1324-1328
DOI: 10.1055/s-0037-1611546
DOI: 10.1055/s-0037-1611546
letter
Ag(I)-Mediated Oxidative Radical Trifluoromethylthiolation of Alkenes
This work was supported by the National Natural Science Foundation of China (Grant No. 21562041 and 21502070) and the Fundamental Research Funds for the Central Universities.Weitere Informationen
Publikationsverlauf
Received: 11. März 2019
Accepted after revision: 29. April 2019
Publikationsdatum:
15. Mai 2019 (online)
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.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611546.
- Supporting Information
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References and Notes
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- 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