E
C. Zheng et al.
Letter
Synlett
X. Y.; Shi, M. Org. Chem. Front. 2017, 4, 86. (e) Li, M.; Petersen, J.
L.; Hoover, J. M. Org. Lett. 2017, 19, 638. (f) Ji, M. S.; Yu, J. J.; Zhu,
C. Chem. Commun. 2018, 54, 6812.
MHz, CDCl3): = 7.93–7.87 (m, 2 H), 7.70–7.64 (m, 2 H), 4.48 (s,
2 H). 13C NMR (101 MHz, CDCl3): = 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): = –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)
(9) (a) Barata-Vallejo, S.; Bonesi, S.; Postigo, A. Org. Biomol. Chem.
2016, 14, 7150. (b) Cheng, Z. F.; Tao, T. T.; Feng, Y. S.; Tang, W. K.;
Xu, J. J.; Dai, J.; Xu, H. J. J. Org. Chem. 2018, 83, 499.
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(c) Huang, Y.; He, X.; Lin, X.; Rong, M.; Weng, Z. Org. Lett. 2014,
16, 3284. (d) Jiang, M.; Zhu, F.; Xiang, H.; Xu, X.; Deng, L.; Yang,
C. Org. Biomol. Chem. 2015, 13, 6935. (e) Zheng, J.; Cheng, R.;
Lin, J. H.; Yu, D. H.; Ma, L.; Jia, L.; Liang, S. H. Angew. Chem. Int.
Ed. 2017, 56, 3196.
(11) (a) Bayreuther, H.; Haas, A. Chem. Ber. 1973, 106, 1418.
(b) Kolasa, A. J. Fluorine Chem. 1987, 36, 29. (c) Alazet, S.;
Zimmer, L.; Billard, T. Chem. Eur. J. 2014, 20, 8589. (d) Glenadel,
Q.; Alazet, S.; Billard, T. J. Fluorine Chem. 2015, 179, 89.
(e) Alazet, S.; Ismalaj, E.; Glenadel, Q.; Bars, D. L.; Billard, T. Eur. J.
Org. Chem. 2015, 4607. (f) Shao, X. Xu C., Lu L., Shen Q. 2015, 80,
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Chem. 2015, 13, 6992.
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): =
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): = 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):
= –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]ace-
tyl}-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclo-
(12) (a) Pan, S.; Huang, Y.; Qing, F. L. Chem. Asian J. 2016, 11, 2854.
(b) Pan, S.; Li, H.; Huang, Y.; Xu, X. H.; Qing, F. L. Org. Lett. 2017,
19, 3247.
penta[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): = 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): = 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):
(13) (a) Shao, X.; Wang, X.; Yang, T.; Lu, L.; Shen, Q. Angew. Chem. Int.
Ed. 2013, 52, 3457. (b) Bootwicha, T.; Liu, X.; Pluta, R.;
Atodiresei, I.; Rueping, M. Angew. Chem. Int. Ed. 2013, 52, 12856.
(c) Wang, X.; Yang, T.; Cheng, X.; Shen, Q. Angew. Chem. Int. Ed.
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Gade, L. H. Chem. Eur. J. 2014, 20, 93. (e) Vinogradova, E. V.;
Müller, P.; Buchwald, S. L. Angew. Chem. Int. Ed. 2014, 53, 3125.
(f) Arimori, S.; Takada, M.; Shibata, N. Org. Lett. 2015, 17, 1063.
(g) Guyon, H.; Chachignon, H.; Tognetti, V.; Joubert, L.; Cahard,
D. Eur. J. Org. Chem. 2018, 3756.
(14) Yadav, A. K.; Singh, K. N. 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.
(16) (a) Liu, H.; Jiang, X. Chem. Asian J. 2013, 8, 2546. (b) Landelle, G.;
Panossian, A.; Leroux, F. R. Curr. Top. Med. Chem. 2014, 14, 941.
(c) Rueping, M.; Liu, X.; Bootwicha, T.; Pluta, R.; Merkens, C.
Chem. Commun. 2014, 50, 2508.
= –41.39 (s,
21H24F3O2S: 397.1449; found: 397.1444
(21) Radical Trapping Experiment
3 F). HRMS (ESI): m/z [M +
H]+ calcd for
C
(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
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 ( = –115.78 ppm) based on 1a. The same
time, the reaction mixture was analyzed by LC–MS
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E