Copper-catalyzed hydroxylation of aryl halides: Efficient synthesis of phenols, alkyl aryl ethers and benzofuran derivatives in neat water

Article abstract of DOI:10.1039/c5gc00871a

A thorough study of environmentally friendly hydroxylation of aryl halides is presented. The best protocol consists of hydroxylation of different aryl bromides and electron-deficient aryl chlorides by water solution of tetrabutylammonium hydroxide catalyzed by Cu₂O/4,7-dihydroxy-1,10-phenanthroline. Various phenol derivatives can be obtained in excellent selectivity and great functional group tolerance. This methodology also provides a direct pathway for the formation of alkyl aryl ethers and benzofuran derivatives in a one-pot tandem reaction.

Full text of DOI:10.1039/c5gc00871a

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Copper-Catalyzed Hydroxylation of Aryl Halides: Efficient
DOI: 10.1039/C5GC00871A
Synthesis of Phenols, Alkyl Aryl Ethers and Benzofuran
Derivatives in Neat Water
a, b a
Yangxin Wang , Chunshan Zhou , Ruihu Wang*
a
a
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences, Fuzhou, Fujian, 350002, China.
Email: ruihu@fjirsm.ac.cn
b
University of Chinese Academy of Sciences, Beijing, 100049, China.
Abstract
A thorough study of environmentally friendly hydroxylation of aryl halides is
presented. The best protocol consists of hydroxylation of different aryl bromides and
electron-deficient aryl chlorides by water solution of tetrabutylammonium hydroxide
catalyzed by Cu2O/4,7-dihydroxy-1,10-phenantroline. Various phenol derivatives can
be obtained in excellent selectivity and great functional group tolerance. This
methodology also provides a direct pathway for the formation of alkyl aryl ethers and
benzofuran derivatives in one-pot tandem reaction.
Keywords: copper, C-O coupling, hydroxylation, green chemistry, water
Introduction
Phenols are very important intermediates in chemical, pharmaceutical and material
1,2
industries. The classical method for preparation of phenols is based on the
decomposition of cumene hydroperoxide with sulfuric acid (Hock process) or the
pyrolysis of sodium salt of benzene sulfonic acid (Dow process). However, both the
protocols suffer from low yield and inefficiency in energy use. Several alternative
methods have been developed for the synthesis of functionalized phenols, such as
nucleophilic aromatic substitution of activated aryl halides, benzyne protocol, as well
3-7
as copper-mediated transformation of arene diazonium salts and arylboronic acids,
but these methods are limited in practical applications because of harsh reaction
conditions, narrow substrate scopes and difficulties in obtaining starting materials.
Recently, some research groups reported the iridium- or palladium-based catalytic
systems for preparing phenols from aryl halides, providing a milder and more

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DOI: 10.1039/C5GC00871A
applicable access to phenols.
However, high price and source scarcity of noble
metals restricts wide use of these catalytic protocols. More recently, it was reported
that phenols could be also synthesized through direct cross-coupling of hydroxide
16, 17
salts and aryl halides catalyzed by copper salts cooperated with organic ligands.
The cheaper copper catalysts appear to potential candidates for replacing noble metal
catalysts in the efficient synthesis of phenols.
Although the reported copper-catalyzed hydroxylation protocols have provided
decent strategies to synthesize phenols, there is still much room to broaden their
applications. For the most reported copper catalytic systems, a well-defined ratio of
water/organic solvent is usually required, and the use of water alone will result in
16-24
unsatisfactory results.
It is well known that water is a cheap and readily available
reaction medium, and the utilization of water-soluble catalytic systems may help
simplify separation, recovery and recycling of the catalysts, especially for the
25
separation of water-insoluble products. However, organic reactions in neat water
breed the additional challenge of water tolerance for the catalyst/ligand systems and
the associated problems of the substrate solubility and reactivity. Recently,
microwave heating has been employed to realize direct conversion of aryl halides to
phenols catalyzed by copper complexes in neat water, but high temperature has been
required and the yields of target products are not satisfactory when aryl bromides
26-28
were used as starting materials.
In other established protocols of copper-catalyzed
direct hydroxylation of aryl halides for preparing phenols in water, significant
limitations, such as long reaction time, high catalyst loading and insufficient
29-32
conversion of electron-rich aryl bromides, are encountered.
As a result, it is highly
desirable to develop new copper-catalyzed strategies for synthesizing phenols under
mild conditions in neat water, especially when inexpensive aryl chlorides are used as
substrates.
It is well known that organic ligands play crucial roles in transition
metal-catalyzed organic reactions. They not only may stabilize metal ions during
reaction and separation, but also can exert important effects on activity and selectivity
of the catalytic systems through their steric and electronic characters as well as
coordination properties to metal ions. In the context, 1,10-phenanthroline and its
derivatives have been extensively employed in copper-catalyzed cross-coupling
33-35
reactions owing to their strong electron-donating ability and ready availability.
The modification of their catalytic performances were achieved through the deliberate

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variation of substituents, but the catalytic applications are mainly focused DoOnI: 1t0h.1e03ir9/C5GC00871A
utilization in organic solvents. The potential utility in neat water is largely limited
owing to their poor solubility in water. Generally, the implementation of catalytic
reactions in water requires the presence of water-soluble or water-dispersed ligands
and catalyst complexes. It is a common strategy to increase hydrophilicity by
attaching ionic groups, such as sulfonate, carboxylate and ammonium, to hydrophobic
ligands. In our previous study, 4,7-dihydroxy-1,10-phenanthroline has been
demonstrated to be a representative candidate, which may serve as an efficient ligand
in the copper-catalyzed Ullmann reaction between aryl bromides and imidazoles in
36
water. The superior promoting effect of 4,7-dihydroxy-1,10-phenanthroline was
attributed to its water solubility under basic conditions. Herein, we extend the
application scope of 4,7-dihydroxy-1,10-phenanthroline, and report a simple and
efficient copper-catalyzed system for direct synthesis of phenols through
hydroxylation of aryl bromides and electron-deficient chlorides under mild conditions
in neat water.
Results and Discussion
The copper-catalyzed hydroxylation reaction was initially evaluated using
bromobenzene as a substrate and 0.2 equivalent of 4,7-dihydroxy-1,10-phenanthroline
(L) as a ligand for optimization of reaction conditions. When the reaction was
performed using 0.1 equivalent of CuI as a copper salt and 0.4 equivalent of CsOH as
o
a nucleophile in neat water at 110 C for 24 h, 66% bromobenzene was converted and
phenol was obtained in a 56% GC yield. Meanwhile, a 10% GC yield of biphenyl
ether was detected as a byproduct (Table 1, entry 1). When the reaction was
conducted in the presence of 0.5 equivalent of tetrabutylammonium bromide (TBAB)
as a phase-transfer catalyst (PTC), bromobenzene afforded a total conversion with the
formation of phenol and biphenyl ether in 80 and 20% GC yields, respectively (entry
2), indicating that PTC is beneficial for this aqueous phase reaction. A total
conversion of bromobenzene was also achieved when KOH was used as a nucleophile
instead of CsOH, but the selectivity of phenol decreased to 63% (entry 3), suggesting
that strong base was favorable for the formation of phenol, which was consistent
37
with the previous reports. To further confirm selectivity-dependent on base, much
weaker base K3PO4 was utilized. As expected, the product is almost totally biphenyl

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ether, though only 39% bromobenzene was transformed (entry 4). DifferenDtOcI:o1p0.p10e3r9/C5GC00871A
salts were also screened. When Cu2O was used, 93% conversion of bromobenzene
and 80% selectivity of phenol were obtained (entry 5), CuO and CuSO4·5H2O gave
quantitative conversion and 82% selectivity of phenol (entries 6 and 7), while CuBr
was inferior to others with a moderate conversion of the substrate (entry 8). In order
to pursue a high conversion along with a high selectivity, the reaction temperature
o
was raised to 130 C in the presence of Cu2O. Unfortunately, the selectivity of phenol
decreased though a full conversion of bromobenzene was observed (entry 9).
However, when the amount of L decreased to 0.1 equivalent, a total conversion of
bromobenzene was achieved and 90% GC yield of phenol was observed by using
o
Cu2O at 110 C (entry 10). Other copper salts were all inferior to Cu2O under the
identical reaction conditions (entries 11~13). When sodium dodecyl sulfate (SDS)
was tested as PTC instead of TBAB, 85% conversion of bromobenzene was obtained
(entry 14). It was known that tetrabutylammonium hydroxide (TBAOH) may act as
both PTC and nucleophile, so 25% and 55% (w/w) aqueous TBAOH were examined,
respectively. To our delight, total conversion of bromobenzene was detected in both
cases, 96% and 98% selectivity of phenol were acquired, respectively (entries 15 and
16). At this stage, a further decrement of the amount of L led to only 36% GC yield of
o
phenol (entry 17). When the reaction temperature was decreased to 100 C, only 88%
bromobenzene was converted, indicating that temperature has an important effect on
hydroxyalation of aryl halides (entry 18). However, no product was detected when
the reaction was performed in air or in the absence of L (entries 19 and 20), implying
that both inert atmosphere and L ligand are necessary in this catalytic system. Thus,
after these attempts, the optimal conditions were 5 mol% Cu2O, 10 mol% L, 1 mL
o
55% aqueous TBAOH at 110 C in N2 atmosphere.
a
Table 1. Screening of reaction conditions for hydroxylation of aryl bromides.
b
Entry
[Cu]
Base
PTC
T
Conversion
[%]
Yield[%]
o
( C)
A
B

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c
1
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CuI
CuI
CsOH
CsOH
KOH
---
110
66
100
100
39
56
80
63
<2
80
82
82
DO1I:010.1039/C5GC00871A
2
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
110
110
110
110
110
110
20
37
37
13
18
18
3
4
5
6
7
CuI
CuI
K3PO4
CsOH
CsOH
CsOH
Cu2O
CuO
93
100
100
CuSO4·5
H2O
8
9
CuBr
Cu2O
Cu2O
CuI
CsOH
CsOH
CsOH
CsOH
CsOH
CsOH
TBAB
TBAB
TBAB
TBAB
TBAB
TBAB
110
130
110
110
110
110
68
100
100
100
39
53
67
90
82
35
41
15
33
10
18
4
d
d
d
d
10
11
12
13
CuO
CuSO4·5
H2O
45
4
d
14
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
CsOH
SDS
---
110
110
110
110
100
110
110
85
100
100
100
88
70
96
98
36
86
0
15
4
d,e
d,f
g
15
16
TBAOH
TBAOH
TBAOH
TBAOH
TBAOH
TBAOH
---
2
17
---
64
<2
0
d,f,h
18
---
d,f,i
19
---
0
j
20
---
0
0
0
a
Reaction conditions: Bromobenzene (0.5 mmol), Base (2.0 mmol), [Cu] (0.025 mmol Cu2O, 0.05mmol for
o
others), L (0.1 mmol), TBAB (0.25 mmol), H2O (1.0 mL), 110 C, N2; GC yields; No PTC was added; L (0.05
b
c
d
e
mmol); 25% aqueous TBAOH solution (2.1 mL/ 4.0 eq); 55% aqueous TBAOH solution (1.0 mL/ 4.0 eq) as
f
g
base; L (0.025 mmol); the reaction temperature was 100 C; the reaction was performed in air; In the absence
h
o
i
j
of L.
With the optimized conditions in hand, the scope and generality of aryl halides
were then investigated, and the results were summarized in Table 2. The
para-substituted electron-rich and electron-deficient aryl bromides afforded the
desirable products in excellent yields (entries 1~7). It seems that the electronic nature
in para-positioned substituents of aryl bromides have no obvious effect on
hydroxylation reaction under the optimized conditions. Excellent yields can be also
achieved
when
electron-rich
meta-methylbromobenzene,

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DOI: 10.1039/C5GC00871A
meta-methoxybromobenzene and 3,5-dimetylbromobenzene were used, the
corresponding target products were obtained in 87, 96 and 85% isolated yields,
respectively (entries 8~10). However, only 48% isolated yield was obtained when
orth-methoxybromobenzene was employed as a substrate, which was probably
attributed to bulkier steric hindrance (entry 11). Interestingly, high yields can be
achieved when both bulky 1-bromonaphthalene and 2-bromonaphthalene were used
(entries 12 and 13). Moreover, carboxyl and hydroxy can be well tolerated in this
catalytic system, the use of para-bromobenzoic acid, para-bromophenol and
meta-bromophenol gave target products in 99, 75 and 86% isolated yields,
respectively (entries 14~16). The use of 1-bromo-4-chlorobenzene gave rise to
4-chlorophenol in an 88% isolated yield, indicating good chemoselectivity between
aryl bromide and chloride (entry 17). It is noteworthy that the catalytic system is also
effective for aryl chlorides bearing electron-withdrawing groups, the use of
para-chlorobenzonitrile and para-chlorobenzoic acid gave the target products in 88
and 99% GC yields, respectively (entries 18 and 19).
Table 2. Synthesis of phenols by copper-catalyzed hydroxylation of arylbromides and
a
chlorides.
b
Yield (%)
Entry
Ar-X
Product
1
94
2
3
99
95
4
5
94
86

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DOI: 10.1039/C5GC00871A
6
7
86
92
8
87
9
96
10
85
Br
11
48
Br
12
94
13
99
14
15
99
75
16
86
17
18
19
88
88
99
a
Reaction conditions: Aryl halides (0.5 mmol), Cu2O (0.025 mmol), L (0.05 mmol), 55% aqueous TBAOH (1.0
o b
mL), 110 C, N2, 24 h; isolated yields.

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DOI: 10.1039/C5GC00871A
By combining with Williamson ether synthesis, the generality of this
hydroxylation methodology was extended for one-pot synthesis of alkyl aryl ethers
15, 17
(Table 3). Compared to previous works by others,
no more PTC and bases were
added in the second step of the one-pot reaction. To our delight, both
electron-deficient and electron-rich aryl bromides provided good to excellent yields to
corresponding alkyl aryl ethers. This procedure offers a straightforward strategy for
the synthesis of alkyl aryl ethers based on two electrophilic components.
a
Table 3. One-pot synthesis of alkyl aryl ethers from aryl bromides
b
R′-X
Yield
Entry
Ar-Br
Product
(%)
1
89
Br
2
84
3
95
4
98
a
Reactions were carried out using Cu2O (5 mol%), L (10 mol%), and aryl bromides (0.5 mmol) in 1 mL aqueous
o
55% TBAOH at 110 C for 24 h. After the reaction mixture was cooled down to ambient temperature, R′-X (1
o b
mmol) was added and the reaction system was kept at 110 C for the additional 24 h. isolated yields.
We also explored application of this catalytic system for the preparation of
substituted benzofuran because benzofuran frameworks are frequently found in a
38,39
variety
of
biologically
active
compounds.
When
1-bromo-2-(phenylethynyl)benzene is submitted to our catalytic protocol (Scheme 1),
2-phenylbenzofuran was obtained in an 80% isolated yield through a sequential

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one-pot tandem reaction involving hydroxylation coupling and subsequent
intramolecular hydroalkoxylation.
Scheme 1. Synthesis of 2-phenylbenzofuran from 2-bromoaryl alkyne.
Conclusion
We have presented a highly efficient method for direct preparation of phenols in neat
water through hydroxylation of aryl bromides and chlorides. Excellent selectivity and
great functional groups tolerance are achieved in the catalytic system. This protocol
also provides a one-pot procedure for the synthesis of alkyl aryl ethers based on two
electrophilic components. Moreover, this methodology is applicable in preparing
benzofuran derivatives through hydroxylation of 1-bromo-2-(phenylethynyl) benzene
and subsequent intramolecular hydroalkoxylation. These promising catalytic
performances may be ascribed to solubility of 4,7-dihydroxy-1,10-phenanthroline
under catalytic conditions in water. In summary, this study not only extends the scope
of copper-catalyzed coupling reaction in water, but also paves a new pathway for the
development of eco-friendly non-precious metal catalytic systems.
Experimental section
33 40
4,7-dihydroxy-1,10-phenanthroline and 1-bromo-2-(phenylethynyl)benzene were
synthesized according to literature methods, other chemicals were purchased from
1
13
commercial suppliers and were used without further purification. H and C NMR
spectra were recorded on a Bruker AVANCE III NMR spectrometer at 400 and 100
MHz, respectively, by using deuterated CDCl3 as locking solvent except otherwise
indicated. Gas chromatography (GC) analyses were performed on a Shimadzu
GC-2014 equipped with a capillary column (RTX-5, 30×0.25 µm) by using a flame
ionization detector.
General procedures for screening reaction conditions in hydroxylation of

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bromobenzene
A 25 mL Schlenk tube equipped with a magnetic stirring bar was charged with copper
salts (0.05 mmol), 4,7-dihydroxy-1,10-phenanthroline (0.1 mmol), base (2 mmol) and
phase-transfer catalyst (0.25 mmol). The tube was evacuated and back-filled with
nitrogen, and this procedure was repeated for three times. After that, bromobenzene
(0.5 mmol) and deionized water (1 mL) was added at a stream of nitrogen, the tube
o
was sealed and stirred in a preheated oil bath (110 C). After 24 h, the reaction
mixture was cooled to ambient temperature, carefully acidified with dilute aqueous
HCl, and extracted with ethyl acetate. The combined organic phase was analyzed with
GC to determine conversion and selectivity. The identity of products was confirmed
by comparison with GC retention times of commercial materials.
General procedures for hydroxylation of aryl halides
A 25 mL Schlenk tube equipped with a magnetic stirring bar was charged with Cu2O
(0.025 mmol), 4,7-dihydroxy-1,10-phenanthroline (0.05 mmol) and aryl halides (0.5
mmol). For solid aryl halides, the tube was evacuated and back-filled with nitrogen,
and this procedure was repeated three times, while for liquid aryl halides, the reaction
components were added after removal of air. After that, 55% aqueous solution of
TBAOH (2 mmol, 1 mL) was added at a stream of nitrogen and the tube was sealed
o
and stirred in a preheated oil bath (110 C). After 24 h, the mixture was cooled to
ambient temperature, carefully acidified with dilute aqueous HCl, and extracted with
ethyl acetate (3×5 mL). The combined organic phase was dried over Na2SO4 and the
solvent was removed under reduced pressure. The crude products were purified by
flash column chromatography on silica gel to afford the desired product. The identity
of the products was confirmed by comparison with literature spectroscopic data.
General procedure for one-pot synthesis of alkyl aryl ethers
A 25 mL Schlenk tube equipped with a magnetic stirring bar was charged with Cu2O
(0.025 mmol), 4,7-dihydroxy-1,10-phenanthroline (0.05 mmol), and aryl halides (0.5
mmol). For solid aryl halides, the tube was evacuated and back-filled with nitrogen,
and this procedure was repeated three times, while for liquid aryl halides, the reaction
components were added after removal of air. After that, 55% aqueous solution of

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TBAOH (2 mmol, 1 mL) was added at a stream of nitrogen, the tube was seDaOleI:d10a.1n03d9/C5GC00871A
o
stirred in a preheated oil bath (110 C) for 24 h. After the mixture was cooled to
ambient temperature, alkyl bromide (1.0 mmol) was added. The reaction mixture was
o
heated at 110 C for another 24 h, then cooled to ambient temperature, diluted with
water and extracted with ethyl acetate (3×5 mL). The combined organic phase was
dried over Na2SO4 and the solvent was removed under reduced pressure. The crude
products were purified by flash column chromatography on silica gel to afford the
desired product. The identity of the products was confirmed by comparison with
literature spectroscopic data.
Synthesis of 2-phenylbenzofuran
A 25 mL Schlenk tube equipped with a magnetic stirring bar was charged with Cu2O
(0.025 mmol), 4,7-dihydroxy-1,10-phenanthroline (0.05 mmol). The tube was
evacuated and back-filled with nitrogen, and this procedure was repeated three times.
After that, 1-bromo-2-(phenylethynyl)benzene (0.5 mmol) and 55% aqueous solution
of TBAOH (2 mmol, 1 mL) were added at a stream of nitrogen, the tube was sealed
o
and stirred in a preheated oil bath (110 C) for 24 h. Then reaction mixture was cooled
to ambient temperature, diluted with water and extracted with ethyl acetate (3×5 mL).
The combined organic layer was dried over Na2SO4 and the solvent was removed
under reduced pressure. The crude products were purified by flash column
chromatography on silica gel to afford the desired product. The identity of the
products was confirmed by comparison with literature spectroscopic data.
Acknowledgements
This work was financially supported by Natural Science Foundation of China
(21273239, 21471151) and Natural Science Foundation of Fujian Province
(2011J01064).
Supporting information
Electronic Supplementary Information (ESI) available: [NMR data and spectra for the

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DOI: 10.1039/C5GC00871A
catalytic products]. See DOI: 10.1039/x0xx00000x
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Green Chemistry
Page 14 of 14
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DOI: 10.1039/C5GC00871A
Table of Contents
An efficient catalytic protocol for hydroxylation of aryl halides in water is proposed
to prepare phenols, ethers and benzofuran derivatives.