Organic Letters
Letter
(2) (a) Gao, G. Y.; Colvin, A. J.; Chen, Y.; Zhang, X. P. J. Org. Chem.
2004, 69, 8886. (b) Gujadhur, R. K.; Venkataraman, D. Tetrahedron Lett.
2003, 44, 81.
(3) (a) Nishiyama, Y.; Tokunaga, K.; Sonoda, N. Org. Lett. 1999, 1,
1725. (b) Nishiyama, Y.; Tokunaga, K.; Kawamatsu, H.; Sonoda, N.
Tetrahedron Lett. 2002, 43, 1507. (c) Bonaterra, M.; Martın, S. E.; Rossi,
R. A. Tetrahedron Lett. 2006, 47, 3511.
(4) (a) Singh, D.; Alberto, E. E.; Rodrigues, O. E. D.; Braga, A. L. Green
Chem. 2009, 11, 1521. (b) Ricordi, V. G.; Freitas, C. S.; Perin, G.;
Lenardao, E. J.; Jacob, R. G.; Savegnago, L.; Alves, D. Green Chem. 2012,
14, 1030. (c) Li, Y.; Wang, H.; Li, X.; Chen, T.; Zhao, D. Tetrahedron
2010, 66, 8583. (d) Reddy, V. P.; Kumar, A. V.; Swapna, K.; Rao, K. R.
Org. Lett. 2009, 11, 951. (e) Chatterjee, T.; Ranu, B. C. J. Org. Chem.
2013, 78, 7145. (f) Taniguchi, N.; Onami, T. J. Org. Chem. 2004, 69, 915.
(g) Ajiki, K.; Hirano, M.; Tanaka, K. Org. Lett. 2005, 7, 4193. (h) Becht,
J. M.; Le Drian, C. J. Org. Chem. 2011, 76, 6327. (i) Saba, S.; Rafique, J.;
Braga, A. L. Adv. Synth. Catal. 2015, 357, 1446.
intermediate E. Meanwhile, deprotonation of indole in the
presence of Cs2CO3 gives nitrogen anion intermediate F and
carbon anion intermediate G. Next, the cross-coupling of radical
E with G affords nitrogen radical cation H. Finally, the single
electron transfer of intermediate H furnishes the desired product.
In summary, we have successfully realized selenium
functionalization at the C3 position of indoles under transition-
metal-free conditions with chemically stable and easily available
elemental selenium as the selenium source. The reaction
proceeds under mild conditions with O2 as the green oxidant.
The 3-selenylindoles derivatives were obtained in moderate to
high yields with excellent functional group tolerance. Studies to
further understand the mechanisms and explore further potential
applications of this reaction in medicinal chemistry are currently
in progress.
(5) (a) Singh, D.; Deobald, A. M.; Camargo, L. R. S.; Tabarelli, G.;
Braga, A. L. Org. Lett. 2010, 12, 3288. (b) Li, Y.; Nie, C.; Wang, H.; Li, X.;
Verpoort, F.; Duan, C. Eur. J. Org. Chem. 2011, 2011, 7331. (c) Zhang, S.
Z.; Karra, K.; Heintz, C.; Kleeker, E.; Jin, J. Tetrahedron Lett. 2013, 54,
4753. (d) Chen, C. H.; Hou, C.; Wang, Y. G.; Andy Hor, T. S.; Weng, Z.
Q. Org. Lett. 2014, 16, 524. (e) Min, L.; Wu, G.; Liu, M. C.; Gao, W. X.;
Ding, J. C.; Huang, X. B.; Wu, H. Y. J. Org. Chem. 2016, 81, 7584. (f) Sun,
P. F.; Jiang, M.; Wei, W.; Min, Y. Y.; Zhang, W.; Li, W. H.; Yang, D. S.;
Wang, H. J. Org. Chem. 2017, 82, 2906. (g) Gao, C.; Wu, G.; Min, L.; Liu,
M. C.; Gao, W. X.; Ding, J. C.; Chen, J. X.; Huang, X. B.; Wu, H. Y. J. Org.
Chem. 2017, 82, 250.
(6) (a) Iwasaki, M.; Tsuchiya, Y.; Nakajima, K.; Nishihara, Y. Org. Lett.
2014, 16, 4920. (b) Qiu, R.; Reddy, V. P.; Iwasaki, T.; Kambe, N. J. Org.
Chem. 2015, 80, 367. (c) Yu, S.; Wan, B.; Li, X. Org. Lett. 2015, 17, 58.
(d) Ricordi, V. G.; Thurow, S.; Penteado, F.; Schumacher, R. F.; Perin,
G.; Lenardao, E. J.; Alves, D. Adv. Synth. Catal. 2015, 357, 933. (e) Zhu,
L.; Qiu, R.; Cao, X.; Xiao, S.; Xu, X.; Au, C.-T.; Yin, S. F. Org. Lett. 2015,
17, 5528.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
Detailed experimental procedures and characterization
Accession Codes
CCDC 1559791 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
(7) (a) Humphrey, G. R.; Kuethe, J. T. Chem. Rev. 2006, 106, 2875.
(b) Hassam, M.; Basson, A. E.; Liotta, D. C.; Morris, L.; van Otterlo, W.
A. L.; Pelly, S. C. ACS Med. Chem. Lett. 2012, 3, 470. (c) Tanaka, H.;
Noguchi, H.; Abe, I. Org. Lett. 2005, 7, 5873.
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ORCID
(8) (a) Ragno, R.; Coluccia, A.; La Regina, G.; De Martino, G.;
Piscitelli, F.; Lavecchia, A.; Novellino, E.; Bergamini, A.; Ciaprini, C.;
Sinistro, A.; Maga, G.; Crespan, E.; Artico, M.; Silvestri, R. J. Med. Chem.
2006, 49, 3172. (b) De Martino, G.; La Regina, G.; Coluccia, A.; Edler,
M. C.; Barbera, M. C.; Brancale, A.; Wilcox, E.; Hamel, E.; Artico, M.;
Silvestri, R. J. Med. Chem. 2004, 47, 6120. (c) La Regina, G.; Edler, M. C.;
Brancale, A.; Kandil, S.; Coluccia, A.; Piscitelli, F.; Hamel, E.; De
Martino, G.; Matesanz, R.; Díaz, J. F.; Scovassi, A. I.; Prosperi, E.;
Lavecchia, A.; Novellino, E.; Artico, M.; Silvestri, R. J. Med. Chem. 2007,
50, 2865. (d) Unangst, P. C.; Connor, D. T.; Stabler, S. R.; Weikert, R. J.;
Carethers, M. E.; Kennedy, J. A.; Thueson, D. O.; Chestnut, J. C.;
Adolphson, R. L.; Conroy, M. C. J. Med. Chem. 1989, 32, 1360. (e) Avis,
I.; Martinez, A.; Tauler, J.; Zudaire, E.; Mayburd, A.; Abu-Ghazaleh, R.;
Ondrey, F.; Mulshine, J. L. Cancer Res. 2005, 65, 4181.
(9) (a) Ferreira, N. L.; Azeredo, J. B.; Fiorentin, B. L.; Braga, A. L. Eur. J.
Org. Chem. 2015, 2015, 5070. (b) Gao, Z.; Zhu, X.; Zhang, R. RSC Adv.
2014, 4, 19891. (c) Azeredo, J. B.; Godoi, M.; Martins, G. M.; Silveira, C.
C.; Braga, A. L. J. Org. Chem. 2014, 79, 4125.
(10) Luo, D. P.; Wu, G.; Liu, M. C.; Gao, W. X.; Huang, X. B.; Chen, J.
C.; Wu, H. Y. J. Org. Chem. 2016, 81, 4485.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We gratefully acknowledge Professor B.-Z. Zhu and Dr. C.-H.
Huang (RCEES, CAS, CN) for helpful discussions, the National
Natural Science Foundation of China (21772137, 21672157,
21372174), the Major Basic Research Project of the Natural
Science Foundation of the Jiangsu Higher Education Institutions
(No. 16KJA150002), the Ph.D. Programs Foundation of PAPD,
the project of scientific and technologic infrastructure of Suzhou
(SZS201708), and Soochow University for financial support. We
thank Fang-Hui Li in this group for reproducing the result for 5a.
(11) Fang, Y.; Zhu, Z.-L.; Xu, P.; Wang, S.-Y.; Ji, S.-J. Green Chem.
2017, 19, 1613.
REFERENCES
■
(12) (a) Asanuma, Y.; Fujiwara, S.; Shin-ike, T.; Kambe, N. J. Org.
Chem. 2004, 69, 4845. (b) Fang, Y.; Wang, S.-Y.; Shen, X.-B.; Ji, S.-J. Org.
Chem. Front. 2015, 2, 1338. (c) Fujiwara, S.-i.; Asanuma, Y.; Shin-ike, T.;
Kambe, N. J. Org. Chem. 2007, 72, 8087.
(1) (a) Mugesh, G.; du Mont, W.; Sies, H. Chem. Rev. 2001, 101, 2125.
(b) Nogueira, C. W.; Zeni, G.; Rocha, J. B. T. Chem. Rev. 2004, 104,
6255. (c) Sarma, B. K.; Mugesh, G. J. Am. Chem. Soc. 2005, 127, 11477.
(d) Bhabak, K. P.; Mugesh, G. Chem. - Eur. J. 2007, 13, 4594. (e) Bhabak,
K. P.; Mugesh, G. Acc. Chem. Res. 2010, 43, 1408. (f) Manjare, S. T.;
Kim, Y.; Churchill, D. G. Acc. Chem. Res. 2014, 47, 2985. (g) Muller, A.;
Cadenas, E.; Graf, P.; Sies, H. Biochem. Pharmacol. 1984, 33, 3235.
(h) Parnham, M.; Sies, H. Expert Opin. Invest. Drugs 2000, 9, 607.
D
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