Ag(I)-Mediated Oxidative Radical Triﬂuoromethylthiolation of Alkenes

Changge Zheng; Yang Liu; Jianquan Hong; Shuai Huang; Wei Zhang; Yupeng Yang; Ge Fang

doi:10.1055/s-0037-1611546

Synlett, Table of Contents

Synlett 2019; 30(11): 1324-1328
DOI: 10.1055/s-0037-1611546

letter

Ag(I)-Mediated Oxidative Radical Triﬂuoromethylthiolation of Alkenes

Changge Zheng *

^aKey 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

^bSchool of Chemical Engineering, Xinjiang Agricultural University, Urumqi 830052, Xinjiang Uygur Autonomous Region, P. R. of China

,

Yang Liu

^aKey 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

^aKey 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

^aKey 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

^bSchool of Chemical Engineering, Xinjiang Agricultural University, Urumqi 830052, Xinjiang Uygur Autonomous Region, P. R. of China

,

Yupeng Yang

^aKey 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

^bSchool of Chemical Engineering, Xinjiang Agricultural University, Urumqi 830052, Xinjiang Uygur Autonomous Region, P. R. of China

› Author Affiliations

Abstract

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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

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References

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

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