Organic Letters
Letter
Yamasaki, M.; Shiro, M.; Shibata, N. J. Am. Chem. Soc. 2013, 135, 8782.
(f) Xu, C.; Ma, B.; Shen, Q. Angew. Chem., Int. Ed. 2014, 53, 9316.
(7) For selected examples see: (a) Teverovskiy, G.; Surry, D. S.;
Buchwald, S. Angew. Chem., Int. Ed. 2011, 50, 7312. (b) Zhang, C.-P.;
Vicic, D. A. J. Am. Chem. Soc. 2012, 134, 183. (c) Tran, L. D.; Popov, I.;
Daugulis, O. J. Am. Chem. Soc. 2012, 134, 18237. (d) 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. (e) Chen, C.; Xie, Y.; Chu, L.;
Wang, R.-W.; Zhang, X.; Qing, F.-L. Angew. Chem., Int. Ed. 2012, 51,
2492. (f) Zhang, C.-P.; Vicic, D. A. Chem. - Asian J. 2012, 7, 1756.
(g) Shao, X.; Wang, X.; Yang, T.; Lu, L.; Shen, Q. Angew. Chem., Int. Ed.
2013, 52, 3457. (h) Matheis, C.; Wagner, V.; Goossen, L. J. Chem. - Eur.
trace 2a is formed. Further mechanistic studies are underway to
fully elucidate the detailed reaction pathway.
In conclusion, we have developed a facile synthetic route to
3-trifluoromethylthiolated coumarins via a silver-mediated oxida-
tive decarboxylative coupling reaction. This protocol is efficient
for a broad substrate scope of readily available substituted
coumarin-3-carboxylic acids in addition to the thiocoumarin
and 3-quinolin-2(1H)-one derivatives. Trifluoromethylthiolated
natural product analogues were also accessed using this method.
We anticipate that this methodology will not only enrich the field
of decarboxylative couplings reactions, but will also provide a
new method for the late-stage synthesis of fluorine-containing
biologically active molecules.
J. 2016, 22, 79. (i) Durr, A. B.; Yin, G.; Kalvet, I.; Napoly, F.;
̈
Schoenebeck, F. Chem. Sci. 2016, 7, 1076.
(8) For selected examples see (a) Yin, F.; Wang, X.-S. Org. Lett. 2014,
́ ́
16, 1128. (b) Fuentes, N.; Kong, W.; Fernandez-Sanchez, L.; Merino, E.;
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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Nevado, C. J. Am. Chem. Soc. 2015, 137, 964. (c) Qiu, Y.-F.; Zhu, X.-Y.;
Li, Y.-X.; He, Y.-T.; Yang, F.; Wang, J.; Hua, H.-L.; Zheng, L.; Wang, L.-
C.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2015, 17, 3694. (d) Jin, D.-P.; Gao,
P.; Chen, D.-Q.; Chen, S.; Wang, J.; Liu, X.-Y.; Liang, Y.-M. Org. Lett.
2016, 18, 3486. (e) Zeng, Y.-F.; Tan, D.-H.; Chen, Y.; Lv, W.-X.; Liu, X.-
G.; Li, Q.; Wang, H. Org. Chem. Front. 2015, 2, 1511.
S
Experimental procedures and characterization data for
starting materials and products (PDF)
Crystallographic data for compound 2j (CIF)
Crystallographic data for compound 2m (CIF)
(9) For reviews see: (a) Rodríguez, N.; Goossen, L. J. Chem. Soc. Rev.
2011, 40, 5030. (b) Shang, R.; Liu, L. Sci. China: Chem. 2011, 54, 1670.
(c) Dai, J.; Wang, G.; Xu, X.; Xu, H. Youji Huaxue 2013, 33, 2460.
(10) For selected works see: (a) Goossen, L.; Deng, G.; Levy, L. Science
2006, 313, 662. (b) Tang, J.; Biafora, A.; Goossen, L. J. Angew. Chem., Int.
Ed. 2015, 54, 13130.
(11) (a) Myers, A. G.; Tanaka, D.; Mannion, M. R. J. Am. Chem. Soc.
2002, 124, 11250. (b) Tanaka, D.; Romeril, S. P.; Myers, A. G. J. Am.
Chem. Soc. 2005, 127, 10323.
(12) Shang, R.; Fu, Y.; Wang, Y.; Xu, Q.; Yu, H. Z.; Liu, L. Angew.
Chem., Int. Ed. 2009, 48, 9350. (b) Cornella, J.; Lu, P.; Larrosa, I. Org.
Lett. 2009, 11, 5506. (c) Hu, P.; Shang, Y.; Su, W. Angew. Chem., Int. Ed.
2012, 51, 5945. (d) Xie, K.; Yang, Z.; Zhou, X.; Li, X.; Wang, S.; Tan, Z.;
An, X.; Guo, C.-C. Org. Lett. 2010, 12, 1564. (e) Zhang, Y.; Patel, S.;
Mainolfi, N. Chem. Sci. 2012, 3, 3196. (f) Li, M.; Hoover, J. M. Chem.
Commun. 2016, 52, 8733.
(13) (a) Hu, F.; Shao, X.; Zhu, D.; Lu, L.; Shen, Q. Angew. Chem., Int.
Ed. 2014, 53, 6105. (b) Pan, S.; Huang, Y.; Qing, F.-L. Chem. - Asian J.
2016, 11, 2854.
AUTHOR INFORMATION
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Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the NSF (CHE-1453879) and West Virginia
University for financial support of this work. NMR spectroscopy
(CHE-1228336) and X-ray crystallography (CHE-1336071)
facilities were partially supported by the NSF. We thank Prof.
Stephen Valentine and Mahdiar Khakinejad of WVU for HRMS
analyses.
(14) (a) Yang, Y.; Liu, Q.-W.; Shi, Y.; Song, Z.-G.; Jin, Y.-H.; Liu, Z.-Q.
Eur. J. Med. Chem. 2014, 84, 1. (b) Xi, G.-L.; Liu, Z.-Q. J. Agric. Food
Chem. 2015, 63, 3516.
(15) (a) Dayam, R.; Gundla, R.; Al-Mawsawi, L. O.; Neamati, N. Med.
Res. Rev. 2008, 28, 118. (b) Kontogiorgis, C. A.; Hadjipavlou-Litina, D. J.
J. Med. Chem. 2005, 48, 6400. (c) Zhao, H.; Donnelly, A. C.; Kusuma, B.
R.; Brandt, G. E. L.; Brown, D.; Rajewski, R. A.; Vielhauer, G.;
Holzbeierlein, J.; Cohen, M. S.; Blagg, B. S. J. J. Med. Chem. 2011, 54,
3839. (d) Symeonidis, T.; Chamilos, M.; Hadjipavlou-Litina, D. J.;
Kallitsakis, M.; Litinas, K. E. Bioorg. Med. Chem. Lett. 2009, 19, 1139.
(e) Bharracharya, B. Res. J. Med. Plant 2011, 5, 116.
REFERENCES
■
(1) Wang, J.; San
́
chez-Rosello,
́
M.; Acena, J. L.; del Pozo, C.;
̃
Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev.
2014, 114, 2432.
(2) Muller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881.
̈
(3) Furuya, T.; Kamlet, A. S.; Ritter, T. Nature 2011, 473, 470.
(4) Barata-Vallejo, S.; Bonesi, S.; Postigo, A. Org. Biomol. Chem. 2016,
14, 7150.
(16) Alazet, S.; Ismalaj, E.; Glenadel, Q.; Le Bars, D.; Billard, T. Eur. J.
Org. Chem. 2015, 2015, 4607.
(17) Although the CF3S radical appears to be a key intermediate under
our conditions, it may not be the direct trifluoromethylthiolating agent
as other CF3S species such as CF3SSCF3 may form in situ as described in
ref 8. See SI for experimental details of reactions with CF3SSCF3.
(18) (a) Minisci, F.; Bernardi, R.; Bertini, F.; Galli, R.; Perchinummo,
M. Tetrahedron 1971, 27, 3575. (b) Duncton, M. MedChemComm 2011,
2, 1135. (c) Kan, J.; Huang, S.; Lin, J.; Zhang, M.; Su, W. Angew. Chem.,
Int. Ed. 2015, 54, 2199.
(19) Zhao, S.; Liu, Y.-J.; Yan, S.-Y.; Chen, F.-J.; Zhang, Z.-Z.; Shi, B.-F.
Org. Lett. 2015, 17, 3338.
(20) (a) Jafarpour, F.; Jalalimanesh, N.; Barzegar, M. B. A.; Olia, A.;
Kashani, A. O. Tetrahedron 2010, 66, 9508. (b) Goossen, L. J.; Linder,
C.; Rodríguez, N.; Lange, P. P.; Fromm, A. Chem. Commun. 2009, 7173.
(c) Lu, P.; Sanchez, C.; Cornella, J.; Larrosa, I. Org. Lett. 2009, 11, 5710.
(5) (a) Nodiff, E. A.; Lipschutz, S.; Craig, P. N.; Gordon, M. J. Org.
Chem. 1960, 25, 60. (b) Kremsner, J. M.; Rack, M.; Pilger, C.; Kappe, C.
O. Tetrahedron Lett. 2009, 50, 3665. (c) Movchun, V. N.; Kolomeitsev,
A. K.; Yagupolskii, Y. L. J. Fluorine Chem. 1995, 70, 255. (d) Billard, T.;
Large, S.; Langlois, B. R. Tetrahedron Lett. 1997, 38, 65. (e) Kieltsch, I.;
Eisenberger, P.; Togni, A. Angew. Chem., Int. Ed. 2007, 46, 754.
(f) Umemoto, T.; Ishihara, S. J. Am. Chem. Soc. 1993, 115, 2156.
(g) Yagupolskii, L. M.; Matsnev, A. V.; Orlova, R. K.; Deryabkin, B. G.;
Yagupolskii, Y. L. J. Fluorine Chem. 2008, 129, 131.
(6) For selected examples see: (a) Ferry, A.; Billard, T.; Langlois, B. R.;
́
Bacque, E. Angew. Chem., Int. Ed. 2009, 48, 8551. (b) Baert, F.; Colomb,
J.; Billard, T. Angew. Chem., Int. Ed. 2012, 51, 10382. (c) Bootwicha, T.;
Liu, X.; Pluta, R.; Atodiresei, I.; Rueping, M. Angew. Chem., Int. Ed. 2013,
52, 12856. (d) Shao, X.; Wang, X.; Yang, T.; Lu, L.; Shen, Q. Angew.
Chem., Int. Ed. 2013, 52, 3457. (e) Yang, Y.-D.; Azuma, A.; Tokunaga, E.;
D
Org. Lett. XXXX, XXX, XXX−XXX