Journal of the American Chemical Society
Page 4 of 5
Chem. Soc., Chem. Commun. 1984, 1984, 793. (d) Popov, V. I.; Boiko,
V. N.; Yagupolskii, L. M. J. Fluorine Chem. 1982, 21, 365.
moiety was reduced to
intramolecular rearrangement and an ammonium salt which
was supposed to be responsible for the
a reactive CF3S species by
1
2
3
4
5
6
7
8
(7) (a) Chen, C.; Xie, Y.; Chu, L.; Wang R. -W.; Zhang, X.; Qing, F. –
L. Angew. Chem. Int. Ed. 2012, 51, 2492. (b) Chen, C.; Chu, L.; Qing, F.
–L. J. Am. Chem. Soc. 2012, 134, 12454. (c) Zhang, C. –P.; Vicic, D. A. J.
Am. Chem. Soc. 2012, 134, 183. (d) Adams, D. J.; Clark, J. H. J. Org.
Chem. 2000, 65, 1456. (e) Clark, J. H.; Jones, C. W.; Kybett, A. P.;
McClinton, M. A. J. Fluorine Chem. 1990, 48, 249. (f) Haas, A.; Nie-
mann, U. Chem. Ber. 1977, 110, 67. (g) Yagupolskii, L. M.; Kondraten-
ko, N. V.; Sambur, V. P. Synthesis, 1975, 1975, 721. (h) Haas, A.; Hell-
wig, V. J. Fluorine Chem. 1975, 6, 521. (i) Sheppard, W. A. J. Org. Chem.
1964, 29, 895. (j) Andreades, S.; Harris, J. F., Jr.; Sheppard, W. A. J.
Org. Chem. 1964, 29, 898.
trifluoromethylthiolation might be generated in the presence
of a amine. The formation of this salt species would be
potential valuable in the asymmetrical reaction when a chiral
amine was used. Our reagent affords not only a success of
trifluoromethylthiolation, but also another potential of
organo-iodine reagents.13a,19 An investigation of the
mechanism of this reaction and expansion of the new reagent
1 to other substrates is underway in our laboratory.
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17
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27
28
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30
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32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(8) (a) Weng, Z.; He, W.; Chen, C.; Lee, R.; Tan, D.; Lai, Z.; Kong, D.;
Yuan, Y.; Huang, K. –W. Angew. Chem. Int. Ed. 2013, 52, 1548. (b)
Tran, L. D.; Popov, I.; Daugulis, O. J. Am. Chem. Soc. 2012, 134, 18237.
(c) Teverovskiy, G.; Surry, D. S.; Buchwald, S. L. Angew. Chem. Int. Ed.
2011, 50, 7312;
(9) (a) Baert, F.; Colomb, J.; Billard, T. Angew. Chem. Int. Ed. 2012, 51,
10382. (b) Ferry, A.; Billard, T.; Bacqué, E.; Langlois, B. R. J. Fluorine
Chem. 2012, 134, 160. (c) Yang, Y.; Jiang, X.; Qing, F. –L. J. Org. Chem.
2012, 77, 7538. (d) Ferry, A.; Billard, T.; Langlois, B. R.; Bacqué, E.
Angew. Chem. Int. Ed. 2009, 48, 8551.
ASSOCIATED CONTENT
Supporting Information
Experimental procedures, characterization data, and copies
1
of H, 19F and 13C NMR spectra. This material is available free
AUTHOR INFORMATION
(10) Shao, X.; Wang, X.; Yang, T.; Lu, L.; Shen, Q. Angew. Chem. Int.
Ed. 2013, 52, 3457.
Corresponding Author
(11) (a) Xu, X.–H.; Taniguchi, M.; Azuma, A.; Liu, G.; Tokunaga, E.;
Shibata, N. Org. Lett. 2013, 15, 686; (b) Xu, X.–H.; Wang, X.; Liu, G.–
K.; Tokunaga, E.; Shibata, N. Org. Lett. 2012, 14, 2544. (c) Xu, X.–H.;
Liu, G.–K.; Azuma, A.; Tokunaga, E.; Shibata, N. Org. Lett. 2011, 13,
4854.
Notes
The authors declare no competing financial interests.
(12) No decomposition of reagent 1 was observed by 1H NMR and 19
F
ACKNOWLEDGMENT
NMR after 4 month storage in refrigerator (about –10 °C). Decompo-
sition was found when reagent 1 was heated in vacuum at 80 °C after
8 h.
(13) (a) Müller, P. Acc. Chem. Res. 2004, 37, 243. (b) Camacho, M. B.;
Clark, A. E.; Liebrecht, T. A.; Deluca, J. P. J. Am. Chem. Soc. 2000, 122,
5210. (c) Hayashi, Y.; Okada, T.; Kawanisi, M. Bull. Chem. Soc. Jpn.
1970, 43, 2506.
This study was financially supported in part by the Platform
for Drug Discovery, Informatics, and Structural Life Science
from the Ministry of Education, Culture, Sports, Science and
Technology, Japan. We are grateful to Central Glass Co., Ltd.
for the gift of triflic acids. We thank the Asahi Glass Founda-
tion for partial support. E.T. acknowledges Grants-in-Aid for
Scientific Research for financial support (24915016).
(14) Hadjiarapoglou, L.; Spyroudis, S.; Varvoglis, A. J. Am. Chem. Soc.
1985, 107, 7178.
(15) (a) Rappoport, Z., eds.; The Chemistry of Enamines (Parts 1 &
2); Wiley: New York, 1994; (b) Xie, J. –H.; Zhu, S. –F.; Zhou, Q. –L.
Chem. Soc. Rev. 2012, 41, 4126; (c) Liu, X.; Cheng, R.; Zhao, F.; Zhang–
Negrerie, D.; Du, Y.; Zhao, K. Org. Lett. 2012, 14, 5480; (d) Valenta, P.;
Carroll, P. J.; Walsh, P. J. J. Am. Chem. Soc. 2010, 132, 14179; (e) Ogawa,
S.; Iida, N.; Tokunaga, E.; Shiro, M.; Shibata, N. Chem. Eur. J. 2010, 16,
7090; (f) Ogawa, Y.; Konishi, T. Chem. Pharm. Bull. 2009, 57, 1110; (g)
Hsiao, Y.; Rivera, N. R.; Rosner, T.; Krska, S. W.; Njolito, E.; Wang, F.;
Sun, Y.; Armstrong, J. D., III; Grabowski, E. J. J.; Tillyer, R. D.; Spin-
dler, F.; Malan, C. J. Am. Chem. Soc. 2004, 126, 9918; (h) Kubryk, M.;
Hansen, K. B. Tetrahedron: Asymmetry 2006, 17, 205; (i) Abdel–
Magid, A. F.; Cohen, J. H.; Maryanoff, C. A. Curr. Med. Chem. 1999, 6,
955; (j) Santilli, A. A.; Bruce, W. F.; Osdene, T. S. J. Med. Chem. 1964,
7, 68.
(16) (a) Gribble G. W., Eds; Heterocyclic Scaffolds II: Reactions and
Applications of Indoles; Springer–Verlag: Berlin, 2010. (b) Barden T. C.
Top. Heterocycl. Chem. 2011, 26, 31;
(17) Sander, W.; Strehl, A.; Winkler, M. Eur. J. Org. Chem. 2001, 2001,
3771.
(18) The trifluoromethylthiolated salt 14 was also found in HRMS-
ESI (see Support Information). When PhNH2 was added as a base in
the trifluoromethylthiolation of indoles, PhNHSCF3 was detected by
19F NMR in the crude mixture.
REFERENCES
(1) (a) Kirsch, P. Modern Fluoroorganic Chemistry: Synthesis, Reac-
tivity, Applications; Wiley–VCH: Weinheim, 2004. (b) Hiyama, T.
Organofluorine Compounds: Chemistry and Properties; Springer–
Verlag: Berlin, 2000. (c) Uneyama, K. Organofluorine Chemistry;
Blackwell: Oxford, U.K., 2006. (d) O’Hagan, D. Chem. Soc. Rev. 2008,
37, 308.
(2) (a) Leroux, F.; Jeschke, P.; Schlosser, M. Chem. Rev. 2005, 105,
827. (b) Stetter, J.; Lieb, F. Angew. Chem. Int. Ed. 2000, 39, 1724. (c)
Manteau, B.; Pazenok, S.; Vors, J. –P.; Leroux, F. R. J. Fluorine Chem.
2010, 131, 140.
(3) Boiko, V. N. Beilstein J. Org. Chem. 2010, 6, 880, and references
cited there.
(4) (a) Kremsner, J. M.; Rack, M.; Pilger, C.; Kappe, C. O. Tetrahe-
dron Lett. 2009, 50, 3665. (b) Nodiff, E. A.; Lipschutz, S.; Craig, P. N.;
Gordon, M. L. J. Org. Chem. 1960, 25, 60. (c) Scherer, O. Angew.
Chem. 1939, 52, 457.
(5) (a) Popput, C.; Medebielle, M.; William, R. D., Jr. Org. Lett. 2004,
6, 301. (b) Blond, G.; Billard, T.; Langlois, B. R. Tetrahedron Lett. 2001,
42, 2473. (c) Large, S.; Roques, N.; Langlois, B. R. J. Org. Chem. 2000,
65, 8848. (d) Billard, T.; Roques, N.; Langlois, B. R. J. Org. Chem. 1999,
64, 3813. (e) Quiclet–Sire, B.; Saicic, R. N.; Zard, S. Z. Tetrahedron Lett.
1996, 37, 9057.
(19) Dohi, T.; Kita, Y. Chem. Commun. 2009, 2009, 2073.
(6) (a) Kieltsch, I.; Eisenberger, P.; Togni, A. Angew. Chem. Int. Ed.
2007, 46, 754. (b) Koshechko, V. G.; Kiprianova, L. A.; Fileleeva, L. L.
Tetrahedron Lett. 1992, 33, 6677. (c) Wakselman, C.; Tordeux, M. J.
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