1
996
Q. Yang et al. / Tetrahedron Letters 54 (2013) 1994–1997
H.; Xiang, T.; Vandenbossche, C. P.; Tanoury, G. J.; Bakale, R. P.; Wald, S. A.
Table 3
Tetrahedron Lett. 1998, 39, 3121.
a
N-arylation of pyrazole in water
4
5
.
.
Yamamoto, T.; Kurata, Y. Can. J. Chem. 1983, 61, 86.
(a) Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901; (b) Hartwig, J.
F. Angew. Chem., Int. Ed. 1998, 37, 2046; (c) Wolfe, J. P.; Wagaw, S.; Marcoux, J.
F.; Buchwald, S. L. Acc. Chem. Res. 1998, 31, 805; (d) Hartwig, J. F. Acc. Chem. Res.
Cu(10%mol), LiOH
TBAB, H2O, 120 C
Ar
X
+
HN
Ar
N
N
N
X=I; Br; Cl;
1998, 31, 852; (e) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576,
1
25; (f) Bellina, F.; Cauteruccio, S.; Mannina, L.; Rossi, R.; Viel, S. J. Org. Chem.
Entry
1
Aryl halide
Product
Yieldb (%)
2005, 70, 3997.
6
.
.
(a) Chan, D. M. T.; Monaco, K. L.; Wang, R. P.; Winters, M. P. Tetrahedron Lett.
1998, 39, 2933; (b) Evans, D. A.; Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39,
I
2
937; (c) Denton, T. T.; Zhang, X.; Cashman, J. R. J. Med. Chem. 2005, 48, 224; (d)
Lam, P. Y. S.; Deudon, S.; Hauptman, E.; Clark, C. G. Tetrahedron Lett. 2001, 42,
427.
N
N
N
82
2
3
a
7
(a) Klapars, A.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 7421; (b)
Lv, X.; Wang, Z.; Bao, W. Tetrahedron 2006, 62, 4756; (c) Panda, N.; Jena, A. K.;
Mohapatra, S.; Rout, S. R. Tetrahedron Lett. 2011, 52, 1924.
H C
H C
3
3
8
.
.
(a) Antilla, J. C.; Baskin, J. M.; Barder, T. E.; Buchwald, S. L. J. Org. Chem. 2004, 69,
2
3
47
53
Br
N
5578; (b) Altman, R. A.; Koval, E. D.; Buchwald, S. L. J. Org. Chem. 2007, 72, 6190.
3b
9
(a) Shafir, A.; Buchwald, S. L. J. Am. Chem. Soc. 2006, 128, 8742; (b) Lv, X.; Bao,
W. J. Org. Chem. 2007, 72, 3863; (c) de Lange, B.; Lambers Verstappen, M. H.;
Vondervoort, L. S.; Sereinig, N.; Rijk, R.; Vries, A. H. M.; Vries, J. G. Synlett 2006,
N
Br
Br
N
3105.
2
a
1
1
0. (a) Zhu, W.; Ma, D. Chem. Commun. 2004, 1934; (b) Zhang, H.; Cai, Q.; Ma, D. J.
Org. Chem. 2005, 70, 5164; (c) Mao, J.; Guo, J.; Song, H.; Ji, S. Tetrahedron 2008,
X = I; Br
78; 44
H3C
N
X
X
N
CH3
4
5
6
4, 1383.
N
N
3c
3d
3e
1. (a) Lu, Z.; Twieg, R. J. Tetrahedron 2003, 44, 6289; (b) Lu, Z.; Twieg, R. J.
Tetrahedron 2005, 61, 903.
N
67
12. (a) Altman, R. A.; Buchwald, S. L. Org. Lett. 2006, 8, 2779; (b) Siddle, J. S.;
Batsanov, A. S.; Bryce, M. R. Eur. J. Org. Chem. 2008, 73, 2746.
N
1
3. (a) Zhu, L. B.; Cheng, L.; Zhang, Y. X.; Xie, R. G.; You, J. S. J. Org. Chem. 2007, 72,
2737; (b) Akhilesh Kumar, V.; Jaspal, S.; Kasi, V. S.; Ritu, C.; Ramesh, C.
Tetrahedron Lett. 2007, 48, 4207; (c) Satoshi, H.; Yusuke, A.; Masahiko, H.
Tetrahedron 2009, 65, 10459.
X = Br; Cl
81; 36
O N
O N
N
6
7
2
2
N
MeO
O
Br
MeO
O
N
68
56
14. Wang, D.; Ding, K. Chem. Commun. 2009, 1891.
5. Haldón, E.; Álvarez, E.; Nicasio, M. C.; Pérez, P. J. Organometallics 2009, 28, 3815.
3
f
N
1
16. (a) Chang, J. W. W.; Xu, X.; Chan, P. W. H. Tetrahedron Lett. 2007, 48, 245; (b)
Rout, L.; Jammi, S.; Punniyamurthy, T. Org. Lett. 2007, 9, 3397; (c) Zhu, L.; Guo,
P.; Li, G.; Lan, J.; Xie, R.; You, J. J. Org. Chem. 2007, 72, 8535; (d) Sperotto, E.;
Vries, J. G.; Klink, G. P. M.; Koten, G. Tetrahedron Lett. 2007, 48, 7366; (e) Zhu, R.;
Xing, L.; Wang, X.; Cheng, C.; Su, D.; Hu, Y. Adv. Synth. Catal. 2008, 350, 1253; (f)
Kubo, T.; Katoh, C.; Yamada, K.; Okano, K.; Tokuyama, H.; Fukuyama, T.
Tetrahedron 2008, 64, 11230; (g) Sreedhar, B.; Arundhathi, R.; Linga Reddy, P.;
Lakshmi Kantam, M. J. Org. Chem. 2009, 74, 7951; (h) Zhu, L. B.; Li, G. C.; Luo, L.;
Guo, P.; Lan, J. B.; You, J. S. J. Org. Chem. 2009, 74, 2200; (i) Yang, Q. C.; Wang, Y.
F.; Zhang, B. J.; Zhang, M. J. Chin. J. Chem. 2012, 30, 2389.
8
9
Br
N
N
3g
NO2
Br
NO2
Me
77
N
N
3h
Me
Br
1
0
1
35
23
17. Correa, A.; Bolm, C. Adv. Synth. Catal. 2007, 349, 2673.
N
1
8. (a) Kim, A. Y.; Lee, H. J.; Park, J. C.; Kang, H.; Yang, H.; Song, H.; Park, K. H.
Molecules 2009, 14, 5169; (b) Kantam, M. L.; Yadav, J.; Laha, S.; Sreedhar, B. J. S.
Adv. Synth. Catal. 2007, 349, 1938.
N
3i
3j
Cl
Cl
Cl
N
1
19. Taillefer, M.; Xia, N.; Oualli, A. Angew. Chem., Int. Ed. 2007, 46, 934.
N
2
0. Huang, H.; Yan, X.; Zhu, W.; Liu, H.; Jiang, H.; Chen, K. J. Comb. Chem. 2008, 10,
17.
6
a
1
0 mol % of activated-Cu, 1.0 equiv of aryl halides/heteroaryl, 1.5 equiv of pyr-
2
1. (a) Yong, F. F.; Teo, Y. C.; Tay, S. H.; Tan, B. Y. H.; Lim, K. H. Tetrahedron Lett.
2011, 52, 1161; (b) Lee, H. W.; Chan, A. S. C.; Kwong, F. Y. Tetrahedron Lett.
2009, 50, 5868.
azole, 0.2 equiv of TBAB, and 2 equiv of LiOH, at 120 °C for 24 h.
b
Isolated yields.
22. (a) Lu, Z. K.; Twieg, R. J. Tetrahedron Lett. 2005, 46, 2997; (b) Röttger, S.; Sjöberg,
P. J. R.; Larhed, M. J. Comb. Chem. 2007, 9, 204.
2
3. (a) Teo, Y. C. Adv. Synth. Catal. 2009, 351, 720; (b) Xie, J. W.; Zhu, X. H.; Huang,
M. N.; Meng, F.; Chen, W. W.; Wan, Y. Q. Eur. J. Org. Chem. 2010, 3219; (c) Li, X.
F.; Yang, D. S.; Jiang, Y. Y.; Fu, H. Green Chem. 2010, 12, 1097; (d) Jiao, J.; Zhang,
X. R.; Chang, N. H.; Wang, J.; Wei, J. F.; Shi, X. Y.; Chen, Z. G. J. Org. Chem. 2011,
Acknowledgment
Financial support from the National Natural Science Foundation
of China (No. 20802049) was greatly acknowledged.
7
6, 1180; (e) Wu, X. M.; Hu, W. Y. Chin. J. Chem. 2011, 29, 2124; (f) Molaei, H.;
Ghanbari, M. G. Chin. Chem. Lett. 2012, 23, 301; (g) Mukhopadhyay, C.; Tapaswi,
P. K. Synth. Commun. 2012, 42, 2217; (h) Wang, D. P.; Zhang, F. X.; Kuang, D. Z.;
Yua, J. X.; Li, J. H. Green Chem. 2012, 14, 1268.
Supplementary data
2
4. (a) Zhu, D.; Wang, R. L.; Mao, J. C.; Xu, L.; Wu, F.; Wan, B. S. J. Mol. Catal. A Chem.
2006, 256, 256; (b) Zhu, R.; Xing, L. X.; Wang, X. Y.; Cheng, C. J.; Su, D. Y.; Hua, Y.
F. Adv. Synth. Catal. 2008, 350, 1253; (c) Kidwai, M.; Mishra, N. K.; Bhardwaj, S.;
Jahan, A.; Kumar, A.; Mozumdar, S. Chem. Cat. Chem. 2010, 2, 1312; (d) Audisio,
D.; Messaoudi, S.; Peyrat, J. F.; Brion, J. D.; Alami, M. J. Org. Chem. 2011, 76,
4995.
2
5. Catalyst preparation. Activated copper powder was prepared by reduction
reaction of CuSO
4
and Zn in water under a violent stirring. Briefly, to a solution
References and notes
of CuSO O (2.5 g, 10 mmol) in 50 mL of distilled water, 0.9 g (13 mmol) of
4
Á5H
2
Zn powder was added slowly at room temperature over a period of 10 min
under a violent stir. During which a brownish red precipitate was formed. After
the action mixture was kept stirring for 1 h, 5 mL (2 mol/L) HCl aqueous
solution was added to get rid of the excessive Zn. After 30 min, the precipitate
was separated by filter and washed with water (3 Â 20 mL). The catalyst was
then washed with ethanol and dried in a vacuum desiccator. 0.56 g of copper
powder was obtained.
1
.
(a) Kundu, N. G.; Mahanty, J. S.; Chowdhurry, C.; Dasgupta, S. K.; Das, B.; Spears,
C. P.; Balzarini, J.; De Clercq, E. Eur. J. Med. Chem. 1999, 34, 389; (b) Almansa, C.;
Bartroli, J.; Belloc, J.; Cavalcanti, F. L.; Ferrando, R.; Gomez, L. A.; Ramis, I.;
Carceller, E.; Merlos, M.; Garcia-Rafanell, J. J. Med. Chem. 2004, 47, 5579.
(a) Smith, W. J.; Sawyer, J. S. Tetrahedron Lett. 1996, 37, 299; (b) Paredes, E.;
Kneeteman, M.; Gonzalez Sierra, M.; Mancini, P. M. E. Tetrahedron Lett. 2003,
2
.
.
44, 2943.
2
6. General procedure: Iodobenzene (1.0 mmol), pyrazole (1.5 mmol), LiOH
3
(a) Yoshikawa, S.; ShinzawaItoh, K.; Nakashima, B.; Yaono, R.; Yamashita, E.;
Inoue, N.; Yao, M.; Fei, M. J.; Libeu, C. P.; Mizushima, T.; Yamaguchi, H.;
Tomizaki, T.; Tsukihara, T. Science 1998, 280, 1723; (b) Hong, Y.; Senanayake, C.
(
2
2.0 mmol), TBAB (0.2 mmol), activated Cu (0.1 mmol), and 2 mL H O were
added to a 10 mL flask, then the flask was sealed by a condenser pipe with
rubber diaphragm on the upper end. The mixture was heated in an oil bath at