3
4
Copper(I)-Catalyzed Highly Efficient Synthesis of
Benzoselenazoles and Benzotellurazoles
fluorescent and photochromic compounds. Therefore, diverse
5
,6
synthetic methods have been developed.
As for the selenium analogues, many selenium-containing
heterocycles including nonfused 1,3-selenazoles possess
biological activities and some 1,3-benzoselenazole derivatives
7
8,9
,
†
‡
Shin-ichi Fujiwara,* Yoshiaki Asanuma,
†
,‡
Tsutomu Shin-ike, and Nobuaki Kambe*
2
are utilized as cyanine dyes. Thus, 1,3-benzoselenazoles are
Department of Chemistry, Osaka Dental UniVersity, Hirakata,
Osaka 573-1121, Japan, and Department of Applied Chemistry,
Graduate School of Engineering, Osaka UniVersity,
Suita, Osaka 565-0871, Japan
expected to have promising importance, but the chemistry of
benzoselenazole still remains much less explored in comparison
to that of benzothiazole. This may be attributed to the lack of
convenient and practical methods for the synthesis of 2-substi-
1
0
tuted benzoselenazoles. For example, the most commonly
employed approach to the construction of the benzoselenazole
ring may be the reaction of zinc bis(o-aminophenylselenoate)
fujiwara@cc.osaka-dent.ac.jp;
1
1
with acid chlorides; however, this method cannot be applied
to the synthesis of the 2-heteroatom-substituted benzoselena-
zoles. Here we describe a highly efficient method for the
ReceiVed June 20, 2007
(
3) Costa, S. P. G.; Ferreira, J. A.; Kirsch, G.; Oliveira-Campos, A. M.
F. J. Chem. Res. 1997, 314-315.
4) Heynderickx, A.; Guglielmetti, R.; Dubest, R.; Aubard, J.; Samat,
A. Synthesis 2003, 1112-1116.
5) For very recent examples: (a) Kawashita, Y.; Ueba, C.; Hayashi,
(
(
M. Tetrahedron Lett. 2006, 47, 4231-4233. (b) Heo, Y.; Song, Y. S.; Kim,
B. T.; Heo, J.-N. Tetrahedron Lett. 2006, 47, 3091-3094. (c) Li, Y.; Wang,
Y.-L.; Wang, J.-Y. Chem. Lett. 2006, 35, 460-461. (d) Evinder, G.; Batey,
R. A. J. Org. Chem. 2006, 71, 1802-1808. (e) Joyce, L. L.; Evindar, G.;
Batey, R. A. Chem. Commun. 2004, 446-447.
A simple and practical useful synthetic method of 1,3-
benzoselenazoles having a heteroatom substituent such as
NRR′, OR, and SR groups at the 2-position was developed
by the copper(I)-catalyzed reaction of 2-bromophenyl (1) or
(
6) For a review: Ulrich, H. In Science of Synthesis: Hetarenes and
Related Ring Systems. FiVe-Membered Hetarenes with One Chalcogen and
One Additional Heteroatom; Schaumann, E., Ed.; George Thieme Verlag:
Stuttgart, Germany, 2002; Vol. 11, pp 835-912.
2-iodophenyl (2) isocyanides with selenium and heteroatom
nucleophiles. In addition, the synthesis of 2-amino-1,3-
benzotellurazoles is also described.
(
7) Reviews for pharmacological activities of selenium-containing
heterocycles: (a) Nogueira, C. W.; Zeni, G.; Rocha, J. B. T. Chem. ReV.
004, 104, 6255-6286. (b) Mugesh, G.; du Mont, W.-W.; Sies, H. Chem.
ReV. 2001, 101, 2125-2180.
8) For biological activities of 1,3-selenazoles: (a) Sekiguchi, A.; Nishina,
2
(
Recently 1,3-benzothiazoles have attracted much attention not
only in synthetic chemistry but also in medicinal and industrial
fields. The benzothiazole ring is an important framework of
pharmacologically active compounds,1 cyanine dyes, and
A.; Kimura, H.; Fukumoto, R.; Kanoh, K.; Ishihara, H.; Koketsu, M. Chem.
Pharm. Bull. 2005, 53, 1439-1442. (b) Koketsu, M.; Choi, S. Y.; Ishihara,
H.; Lim, B. O.; Kim, H.; Kim, S. Y. Chem. Pharm. Bull. 2002, 50, 1594-
1
596. (c) Li, H.; Hallows, W. H.; Punzi, J. S.; Marquez, V. E.; Carrell, H.
2
L.; Pankiewicz, K. W.; Watanabe, K. A.; Goldstein, B. M. Biochemistry
1
994, 33, 23-32. (d) Goldstein, B. M.; Leary, J. F.; Farley, B. A.; Marquez,
†
Osaka Dental University.
Osaka University.
V. E.; Levy, P. C.; Rowley, P. T. Blood 1991, 78, 593-598.
‡
(9) For recent examples of the synthesis of 1,3-selenazoles: (a) Narender,
M.; Reddy, M. S.; Kumar, V. P.; Reddy, V. P.; Nageswar, Y. V. D.; Rao,
K. R. J. Org. Chem. 2007, 72, 1849-1851. (b) Koketsu, M.; Kanoh, K.;
Ando, H.; Ishihara, H. Heteroatom Chem. 2006, 17, 88-92. (c) Below,
H.; Pfeiffer, W.-D.; Geisler, K.; Lalk, M.; Langer, P. Eur. J. Org. Chem.
2005, 3637-3639. (d) Koketsu, M.; Tanaka, H.; Ishihara, H. Chem. Lett.
2005, 34, 1260-1261. (e) Geisler, K.; Pfeiffer, W.-D.; K u¨ nzler, A.; Below,
H.; Bulka, E.; Langer, P. Synthesis 2004, 875-884. (f) Geisler, K.; K u¨ nzler,
A.; Below, H.; Bulka, E.; Pfeiffer, W.-D.; Langer, P. Synthesis 2004, 97-
105. (g) Geisler, K.; Pfeiffer, W.-D.; M u¨ ller, C.; Nobst, E.; Bulka, E.;
Langer, P. Synthesis 2003, 1215-1220. (h) Geisler, K.; K u¨ nzler, A.; Below,
H.; Bulka, E.; Pfeiffer, W.-D.; Langer, P. Synlett 2003, 1195-1197. (i)
Zhang, P.-F.; Chen, Z.-C. Synthesis 2000, 1219-1222. (j) Maeda, H.;
Kambe, N.; Sonoda, N.; Fujiwara, S.; Shin-ike, T. Tetrahedron 1997, 53,
13667-13680. For reviews: (k) Pfeiffer, W.-D. In Science of Synthesis:
Hetarenes and Related Ring Systems. FiVe-Membered Hetarenes with One
Chalcogen and One Additional Heteroatom; Schaumann, E., Ed.; George
Thieme Verlag: Stuttgart, Germany, 2002; Vol. 11, pp 941-989. (l) Larsen,
R. D. In ComprehensiVe Heterocyclic Chemistry II; Shinkai, I., Ed.;
Pergamon: New York, 1996; Vol. 3, pp 493-510.
(
1) For recent examples: (a) Mortimer, C. G.; Wells, G.; Crochard, J.-
P.; Stone, E. L.; Bradshaw, T. D.; Stevens, M. F. G.; Westwell, A. D. J.
Med. Chem. 2006, 49, 179-185. (b) Brantley, E.; Antony, S.; Kohlhagen,
G.; Meng, L.-H.; Agama, K.; Stinton, S. F.; Sausville, E. A.; Pommier, Y.
Cancer Chemother. Pharmacol. 2006, 58, 62-72. (c) Ryu, C.-K.; Han,
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Chem. 2004, 11, 1009-1021. (e) Mathis, C. A.; Wang, Y.; Holt, D. P.;
Huang, G.-F.; Debnath, M. L.; Klunk, W. E. J. Med. Chem. 2003, 46, 2740-
2
754. (f) Ko cˇ ´ı , J.; Klime sˇ ov a´ , V.; Waisser, K.; Kaustov a´ , J.; Dahse, H.-
M.; M o¨ llmann, U. Bioorg. Med. Chem. Lett. 2002, 12, 3275-3278. (g)
Mouri, T.; Tokumura, J.; Kochi, S.; Fukui, H.; Nakano, J.; Ando, T.; Hori,
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1
1
Chem. 2001, 8, 203-210. (k) Oketani, K.; Inoue, T.; Murakami, M. Eur.
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(2) For recent examples: (a) Santos, P. F.; Reis, L. V.; Almeida, P.;
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ditional Heteroatom; Schaumann, E., Ed.; George Thieme Verlag: Stuttgart,
Germany, 2002; Vol. 11, pp 991-999.
(11) For example: Bogert, M. T.; Stull, A. J. Am. Chem. Soc. 1927, 49,
2011-2016.
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(
1
c) Reis, L. V.; Serrano, J. P. C.; Almeida, P.; Santos, P. F. Synlett 2002,
617-1620.
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0.1021/jo7013164 CCC: $37.00 © 2007 American Chemical Society
Published on Web 09/15/2007
J. Org. Chem. 2007, 72, 8087-8090
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