J. Chen et al. / Catalysis Communications 12 (2011) 1463–1465
1465
Table 3
was important to stress that the hydroxylation reactions above could
tolerate various functional groups, including C–Cl bond (Table 3,
Entries 2, 3), C–F bond (Table 3, Entry 4, 5), carboxyl groups (Table 3,
Entries 7, 8), aldehyde group (Table 3, Entry 9), and hydroxyl group
(Table 3, Entry 10) in aryl halides.
Copper-catalyzed synthesis of substituted phenols by hydroxylation of aryl bromides.
CuI (0.1 equiv.)
KOH (6.0 equiv.)
Br
OH
R
PEG-400/H O (4:1)
2
R
o
1
20 C, 8 h
Entrya
1
ArBr
ArOH
Yieldb (%)
4. Conclusions
c
54 , 93
Br
OH
We have developed a general, economical and efficient protocol for
copper-catalyzed synthesis of substituted phenols by hydroxylation of
aryl iodides and even less reactive aryl bromides under mild conditions.
This procedure avoids the otherwise typical formation of the related
biaryl ether byproduct. This method is of particular value given its
experimental simplicity, functional group compatibility, and the low
cost of the catalytic system, which makes this method readily adaptable
to production on an industrial scale, where safety and environmental
factors are of particular concern. Further application of the CuI/PEG-400
catalytic system is currently under investigation in our laboratory.
2
Br
OH
91
Cl
Cl
3
4
89
88
Cl
Br
Cl
OH
Br
OH
F
F
5
94
88
92
F
Br
Br
Br
Br
F
OH
OH
Acknowledgments
6
Br
This project was sponsored by the Jiangxi Provincial Natural
Science Foundation (Nos. 2010GQH0064). We also thank the Analysis
and Testing Center of Jiangxi Normal University for NMR
measurements.
7 d
OH
COOH
COOH
8d
95
Br
OH
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a
Reaction conditions: aryl bromides (1 mmol), CuI (0.1 mmol), KOH (6 mmol),
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d
e