An Efficient Palladium and Bis(2-pyridylmethyl)amine-based System
Table 3 The Suzuki-Miyaura reactions of aryl halides with
arylboronic acidsa
References
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PdCl2:1 = 1:2
X
R'
B(OH)2
+
K2CO3, H2O, r.t.
R
R'
R
Catalyst/ T/ Time/ Yieldb/
Entry
R
H
X
R'
mol%
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0. 1
℃
h
%
98
99
99
99
99
95
97
81
89
96
98
83
99
99
99
95
1
2
3
4
5
6
7
8
9
Br
H
H
H
H
H
H
H
H
H
H
H
H
r.t. 1.5
r.t. 1.5
r.t. 1.5
r.t. 1.5
r.t. 1.5
r.t. 1.5
r.t. 1.5
4-MeCO Br
4-CHO Br
4-CN Br
4-NO2 Br
4-MeO Br
4-Me Br
2-MeCO Br
r.t.
80
80.
80
80
2
3
3
3
4
H
Cl
10 4-MeCO Cl
0.1
11
12
13
14
15
16
4-NO2 Cl
4-Me Cl
0.1
0.1
H
H
H
H
Br 4-NO2
0.01
0.01
0.01
0.01
r.t. 1.5
r.t. 1.5
r.t. 1.5
Br 4-CH3O
Br 4-MeCO
Br 4-Me
r.t.
2
a
General reaction conditions: aryl halides (1 mmol), arylboronic
acid (1.5 mmol), H2O (3 mL), K2CO3 (2 mmol), PdCl2/1=1∶2,
under air condition. The reaction was monitored by TLC. Iso-
b
lated yield.
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0.1 mol% catalyst at 80 ℃ (Table 3, Entries 11—14).
And excellent yields could be also obtained for the cou-
pling of aryl bromide with various substituted arylbo-
ronic acid at room temperature within 2 h (Table 3, En-
tries 15, 16).
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Conclusions
In conclusion, we reported the successful synthesis
of bis(2-pyridylmethyl)amine-based compoud 1, an ef-
fective ligand for Suzuki-Miyaura cross-coupling reac-
tion. It is demonstrated that a wide range of aryl halides,
including aryl bromides and even aryl chlorides, could
couple with arylboronic acids smoothly by using this
water-soluble catalyst PdCl2/1 in water under air condi-
tion with the catalyst loading of 0.01—0.1 mol%. Fur-
thermore, this catalytic system could tolerate a broad
range of functional groups.
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2007, 48, 163.
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Acknowledgement
[15] (a) Arvela, R. K.; Leadbeater, N. E.; Sangi, M. S.; Williams, V. A.;
Granados, P.; Singer, R. D. J. Org. Chem. 2005, 70, 161; (b)
Gil-Molto, J.; Karlstrom, S.; Najera, C. Tetrahedron 2005, 61,
12168; (c) Korolev, D. N.; Bumagin, N. A. Tetrahedron Lett. 2005,
This work was financially supported by the National
Natural Science Foundation of China (No. 20672035).
Chin. J. Chem. 2012, 30, 1114—1118
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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