J. Qiu et al. / Tetrahedron Letters 52 (2011) 6489–6491
6491
Table 3 (continued)
Entry
10
RX (1)
R0B(OH)2 (2)
Time (min)
3
Product (3)
Yieldb (%)
1c
2a
3c
99
CN
11
12
13
14
1d
2a
3
5
99
(3j)
OHC
Cl
Br
CHO
2a
97
99
97
(1f)
(3k)
Br
Cl
2a
5
(1e)
(3l)
Br
B(OH)2
B(OH)2
Br
OMe
1c
30
(2e)
(3m)
15
16
1b
30
5
91
98
(2f)
(3n)
1d
2f
CN
(3o)
Br
O
O
17
18
2a
60
87
85
(1g)
(3p)
B(OH)2
S
MeO
1c
120
(3q)
S
(2g)
19
20
2a
2c
120
120
70
N
(3r)
N
Br
(1h)
Cl
3c
10c
(1j)
a
Reaction conditions: aryl bromides (0.5 mmol), arylboronic acids (0.75 mmol), PdCl2 (0. 5 mol %), K2CO3 (1 mmol), 50% EtOH (4 mL), room temperature, in air. The
reaction was monitored by TLC.
b
Isolated yield.
Reaction was performed at 60 °C.
c
1999, 121, 9550; (d) Suzuki, A. J. Org. Chem. 2002, 653, 83; (e) Phan, N. T. S.;
Sluys, M. V. D.; Jones, C. W. Adv. Synth. Catal. 2006, 348, 609; (f) Suzuki, A. Chem.
Commun. 2005, 4759.
Conclusions
In summary, we have successfully developed a simple and effi-
cient protocol for the PdCl2-ligandless Suzuki coupling of aryl bro-
mides with arylboronic acids. The advantages of this procedure are
simple operation, good to excellent yields, short reaction time, ab-
sence of ligands, and mild and environmentally friendly conditions.
A great diversity of substrates were tolerated for this method.
3. (a) Kostas, I. D.; Andreadaki, F. J.; Kovala-Demertzi, D.; Prentjas, C.; Demertzis,
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Acknowledgments
This research was financially supported by the National Nature
Science Foundation of China (20672035) and Key Laboratory of
Organofluorine Chemistry, Shanghai Institute of Organic Chemis-
try, Chinese Academy of Sciences.
Supplementary data
7. Zhang, P. P.; Zhang, X. X.; Sun, H. X.; Liu, R. H.; Wang, B.; Lin, Y. H. Tetrahedron
Lett. 2009, 50, 4455.
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Supplementary data associated with this article can be found, in
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