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Synlett 2019; 30(11): 1324-1328
DOI: 10.1055/s-0037-1611546
letter
© Georg Thieme Verlag Stuttgart · New York

Ag(I)-Mediated Oxidative Radical Trifluoromethylthiolation of Alkenes

Changge Zheng  *
a   Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, P. R. of China   Email: cgzheng@jiangnan.edu.cn
b   School of Chemical Engineering, Xinjiang Agricultural University, Urumqi 830052, Xinjiang Uygur Autonomous Region, P. R. of China
,
Yang Liu
a   Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, P. R. of China   Email: cgzheng@jiangnan.edu.cn
,
Jianquan Hong
a   Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, P. R. of China   Email: cgzheng@jiangnan.edu.cn
,
Shuai Huang
a   Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, P. R. of China   Email: cgzheng@jiangnan.edu.cn
,
Wei Zhang
b   School of Chemical Engineering, Xinjiang Agricultural University, Urumqi 830052, Xinjiang Uygur Autonomous Region, P. R. of China
,
Yupeng Yang
a   Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, P. R. of China   Email: cgzheng@jiangnan.edu.cn
,
Ge Fang
b   School of Chemical Engineering, Xinjiang Agricultural University, Urumqi 830052, Xinjiang Uygur Autonomous Region, P. R. of China
› Author AffiliationsThis 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.
Further Information

Publication History

Received: 11 March 2019

Accepted after revision: 29 April 2019

Publication Date:
15 May 2019 (online)

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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

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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  • 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