General copper-catalyzed transformations of functional groups from arylboronic acids in water

Article abstract of DOI:10.1002/chem.201003711

A simple and general copper-catalyzed method has been developed for transformations of various functional groups (i I, i N₃, i SO₂R, i OH, i NH₂, and i NO ₂) on aromatic rings from arylboronic acids in water under air. The protocol uses cheap and readily available inorganic salts (KI, NaN₃, NaSO₂R, NaOH, NaNO₂) and aqueous ammonia as the functional-group sources, simple Cu₂O/NH₃ as the catalyst system, environmentally friendly water as the solvent, and oxygen in air as the oxidant. Importantly, the copper catalyst system in water was recyclable. This study should provide a useful strategy for interconversions of the functional groups on aromatic rings.

Full text of DOI:10.1002/chem.201003711

DOI: 10.1002/chem.201003711
General Copper-Catalyzed Transformations of Functional Groups from
Arylboronic Acids in Water
Haijun Yang, Yong Li, Min Jiang, Junmei Wang, and Hua Fu*[a]
Abstract:
A
simple and general
NaN3, NaSO2R, NaOH, NaNO2) and
aqueous ammonia as the functional-
group sources, simple Cu2O/NH3 as the
catalyst
system,
environmentally
copper-catalyzed method has been de-
veloped for transformations of various
functional groups ( I, N3, SO2R,
friendly water as the solvent, and
oxygen in air as the oxidant. Impor-
tantly, the copper catalyst system in
water was recyclable. This study should
provide a useful strategy for intercon-
versions of the functional groups on ar-
omatic rings.
À
À
À
À
À
À
OH, NH2, and NO2) on aromatic
rings from arylboronic acids in water
under air. The protocol uses cheap and
readily available inorganic salts (KI,
Keywords: boron · catalysis · cop-
per · functional-group transforma-
tions · water chemistry
Introduction
lysts, organic solvents, and specific temperatures, and the
limited substrate scope and unrecyclable catalyst systems
greatly limit use of these methods. In modern organic syn-
thesis, the ideal reaction conditions include the use of cheap,
highly efficient and recyclable catalyst systems, environment
friendly water as the solvent, room temperature reactions
under air (without extrusion of air) and easy workup proce-
dures after reactions. Herein, we report general transforma-
Aromatic compounds are ubiquitous in the world[1] and
their properties are highly dependent on the functional
groups of their aromatic rings. For example, aryl halides,[2]
azides,[3] sulfones,[4] phenols,[5] arylamines,[6] and nitro-
ACHTUNGTRENNUNG
arenes[7] are widely used as chemicals, synthetic intermedi-
ates, pharmaceuticals, natural products, and materials.
Therefore, the functional-group transformation is an impor-
tant and long-term direction in chemistry. In the past several
decades, transition-metal-catalyzed transformations of aro-
matic halides and tosylates have been powerful methods in
the synthesis of, for example, palladium or copper-catalyzed
aryl iodides,[8] azides,[9] sulfones,[10] phenols,[11] arylamines,[12]
and nitroarenes.[13] However, some shortcomings appear
with them, such as the use of expensive, toxic catalysts and
ligands for palladium catalysis or harsh reaction conditions,
and limited substrate scope for copper catalysis. Aryl boron
compounds are common chemicals and they are easily pre-
pared from readily available aryl halides (such as aryl bro-
À
À
À
tions
of
functional
groups
( I,
N3,
SO2R,
À
À
À
OH, NH2, and NO2) on aromatic rings from arylboronic
acids under the ideal conditions above.
Results and Discussion
It is well known that aryl iodides usually show much higher
reactivity than the corresponding aryl bromides and chlor-
ides in the coupling reactions, and some aryl iodides, such as
125I-radiolabeled arenes, show many important applications
in pharmacology, medicine, and biochemistry.[23] Unfortu-
nately, direct iodination of arenes with iodine is difficult be-
cause of the low reactivity of iodine towards the electrophil-
ic substitution.[24] Therefore, it is very desirable to develop a
highly efficient approach to aryl iodides. Considering the
ready availability and low toxicity of copper catalysts, we
first investigated copper-catalyzed iodination of arylboronic
acids in water.
As shown in Table 1, phenylboronic acid (1a) was chosen
as the model substrate at room temperature to optimize the
reaction conditions including catalysts, ligands/additives, sol-
vents, and temperature. CuI and Cu2O (0.1 equiv relative to
the amount of 1a) were used as the catalysts in water in the
presence of five equivalents of KI (Table 1, entries 1 and 2),
and only a trace amount of iodobenzene was detected. Vari-
ous copper/ammonia catalyst systems (0.1 equiv) were
screened (preparation of copper/ammonia catalyst systems:
a mixture of copper salt (0.1 equiv) and aqueous ammonia
mides and chlorides) and tosylates[14] or by iridium-catalyzed
direct borylations of arenes through C H bond activation.
[15]
À
The aryl boron compounds have been used as the starting
materials to make aromatic compounds containing various
functional groups (including aryl halides,[16] aryl azides,[17]
aryl sulfones,[18] phenols,[19] arylamines developed by us[20]
and nitroarenes[21]) through an aerobic oxidative strategy.[22]
Unfortunately, the methods need the special ligands of cata-
[a] H. Yang, Prof. Dr. Y. Li, M. Jiang, J. Wang, Prof. Dr. H. Fu
Key Laboratory of Bioorganic Phosphorus Chemistry
and Chemical Biology (Ministry of Education)
Department of Chemistry, Tsinghua University
Beijing 100084 (P.R. China)
Fax : (+86)10-62781695
E-mail: fuhua@mail.tsinghua.edu.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201003711.
5652
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5652 – 5660

FULL PAPER
Table 1. Copper-catalyzed iodination of phenylboronic acid to iodoben-
zene: optimization of conditions.[a]
Table 2. Copper-catalyzed synthesis of aryl iodides, azides, sulfones, and
phenols.[a]
Entry Cat.
NH3·H2O [mmol] Solvent MI [mmol] Yield [%][b]
1
2
3
4
5
6
7
8
CuI
Cu2O
CuI
Cu2O
CuO
–
–
2.5
2.5
2.5
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
KI (5)
KI (5)
KI (5)
KI (5)
KI (5)
KI (5)
KI (5)
KI (5)
KI (5)
trace[c]
trace[c]
80
92
76
70
12
70
81
72
66
trace
89
CuN
A: aryl iodides
CuSO4
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
2.5
1
2
2.5
2.5
2.5
2.5
2.5
2.5
2.5
9
10
11
12
13
14
15
16
MeOH KI (5)
CH3CN KI (5)
DMF
H2O
H2O
H2O
H2O
KI (5)
NaI (5)
KI (2)
KI (5)
KI (5)
58
57[d]
trace[e]
[a] Reaction conditions: phenylboronic acid (1 mmol), catalyst
(0.1 mmol), solvent (2 mL) under air; reaction time: 24 h; reaction tem-
perature: ~258C. [b] Yield determined by 1H NMR spectroscopy. [c] No
addition of NH3·H2O. [d] Reaction temperature: 408C. [e] Under a nitro-
gen atmosphere.
B: aryl azides
(2.5 equiv) was stirred for 30 min under air; entries 3–7) and
the Cu2O/NH3 catalyst system showed the best activity
(92% conversion yield; entry 4). To our satisfaction, only
trace amounts of aniline were observed in the resulting solu-
tion, and a possible reason for this is that more of the IÀ ion
and the higher nucleophilic power of the IÀ ion relative to
ammonia led to the formation of the major product (iodo-
benzene). Here, ammonia could act as the ligand of the
copper catalyst and additive. Reaction yields decreased
when the amount of aqueous ammonia was reduced (en-
tries 8 and 9). The effect of solvents was investigated (com-
pare entries 4, 10–12) and water was the best solvent
(entry 4). The result can be attributed to the good dissolving
power of the substrates (phenylboronic acid and KI) and
copper catalyst system (Cu2O/NH3) in water. A slightly
lower yield (89%) was provided when NaI replaced KI as
the iodic source (entry 13). The yield decreased when the
amount of KI was reduced (entry 14). The reaction provided
only a 57% yield with more phenol appearing when the
temperature was raised to 408C (entry 15). Only a trace
amount of iodobenzene was found in the absence of air
(under nitrogen atmosphere; entry 16) and the result indi-
cated that an oxidative process was involved in the forma-
tion of iodobenzene.[22] Therefore, the optimal reaction con-
ditions for the synthesis of aryl iodides are as follows: KI as
the iodic source (5 equiv), Cu2O/NH3 complex as the cata-
lyst system (0.1 equiv), water as the solvent, and the reac-
tion was carried out under air at room temperature
C: aryl sulfones
D: phenols
[a] Reaction conditions: reaction temperature: ~258C; reaction time:
24 h (for the synthesis of aryl iodides), ArB(OH)2 (1 mmol), KI
(5 mmol), NaN3 (5 mmol), RSO2Na (5 mmol), NaOH (3 mmol), Cu2O
(0.1 mmol), NH3·H2O (2.5 mmol), water (2 mL) under air. Yields shown
are the yields of the isolated product.
ACHTUNGTRENNUNG
tion of arylboronic acids. As shown in Table 2A, the sub-
strates examined provided good to excellent yields. Elec-
Chem. Eur. J. 2011, 17, 5652 – 5660
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5653

H. Fu et al.
tronic variation in the arylboronic acids, including electron-
withdrawing, neutral, and electron-donating effects, did not
obviously affect the efficiency of the reactions. Iodination of
(E)-styrylboronic acid was also investigated and the corre-
sponding target product, (E)-1-(2-iodovinyl)benzene (2r),
was obtained in 80% yield under the standard conditions.
Therefore, the present method is suitable for the synthesis
of alkenyl iodides.
Inspired by the excellent results from iodination of aryl-
boronic acids above, we used the same copper catalyst
system (Cu2O/NH3) to make aryl azides, sulfones, and phe-
nols (see Table2B–D). Fortunately, the copper-catalyst
system worked well when using NaN3, NaSO2R (R=Me,
Ph, PhMe), and NaOH as the functional-group sources. The
tested substrates also provided good to excellent yields and
the arylboronic acids containing electron-donating groups
showed higher reactivity than the ones containing electron-
withdrawing groups. Similarly, the copper catalyst system
(Cu2O/NH3) was also suitable for azidonation and sulfonyl-
the coupling reactions. Compared with the synthesis of phe-
nols, more NH3·H2O and less NaOH were required for the
amination of arylboronic acids. The tested substrates provid-
ed the corresponding arylamines in good to excellent yields
(see Table 3A). We used the catalyst system (0.1 equiv
Cu2O/2.5 equiv NH3·H2O) to perform ipso-nitration of phe-
nylboronic acid with NaNO2, and the reaction provided ni-
trobenzene in only 36% yield. We made a slight change for
the copper catalyst system, the experiments showed that
Cu2O (0.1 equiv)/NH3·H2O (1.8 equiv; relative to the
amount of arylboronic acids) was a better ratio, and the cat-
alyst system did not need a previous 30 min stirring. As
shown in Table 3B, the aerobic oxidative couplings of aryl-
boronic acids with NaNO2 provided the corresponding nitro-
arenes in moderate to good yields. Arylboronic acids con-
taining electron-donating groups were of higher reactivity
than ones containing electron-withdrawing groups during
the amination and ipso-nitration of arylboronic acids above.
The transformations of functional groups above all
showed excellent tolerance of functional groups including
carbon–halo bonds, ether, nitro, hydroxyl, amino, aldehyde,
nitrile, amine, and carboxyl. In addition, the workup proce-
dure was very simple, most of the target products were puri-
fied by extraction from the aqueous solutions with ethyl ace-
tate and the others were obtained by column chromatogra-
phy on silica gel. Therefore, the general and easy workup
method showed many advantages over the previous meth-
ods.
Importantly, the copper catalyst system in water is recy-
clable for the transforms of functional groups from arylbor-
onic acids. As shown in Table 4, phenylboronic acid was
chosen as the model substrate to investigate reuse of the
copper catalyst system. For example, the resulting solution
was extracted with ethyl acetate (3ꢁ2 mL) after the first io-
dination of phenylboronic acid completed and the remaining
catalyst system in water could be reused in the following io-
dination of phenylboronic acid. The yields from the second
to fourth cycle were 74, 72, and 72%, respectively. The
other functionalizations of arylboronic acids also provided
good recyclable results as shown in Table 4.
ACHTUNGTRENNUNGation of (E)-styrylboronic acid (see 3o and 4d in Ta-
ble 2B,C).
We further performed amination and ipso-nitration of ar-
ylboronic acids under similar copper catalytic conditions as
shown in Table 3. For the amination of arylboronic acids,
nine equivalents of NH3·H2O were added to the solution, in
which ammonia acted as ligand/additive and substrate. The
experiment showed that addition of an extra strong base
(such as 1 equiv of NaOH) was necessary because nucleo-
philic attack of ammonia was helpful in base medium during
Table 3. Copper-catalyzed synthesis of arylamines and nitroarenes.[a]
A: aryl iodides
Table 4. Yields from the first to fourth cycle under Cu2O/NH3 catalysis in
water.[a]
B: nitroarenes
Functional group First [%] Secondary [%] Third [%] Fourth [%]
ÀI
82
87
84
92
90
68
74
78
76
85
82
55
72
76
72
82
78
54
72
74
70
82
76
51
ÀN3
ÀSO2R
ÀOH
ÀNH2
ÀNO2
[a] Reaction conditions: reaction temperature: ~258C, ArB(OH)2
(1 mmol), NaNO2 (7 mmol), Cu2O (0.1 mmol), NH3·H2O (9.0 mmol for
the synthesis of arylamines, 1.8 mmol for the synthesis of nitroarenes),
and water (2 mL) under air.
[a] Isolated product yield.
5654
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5652 – 5660

Copper-Catalyzed Transformations
FULL PAPER
The combined organic phase was dried over anhydrous MgSO4 and fil-
tered and the solvent of the filtrate was removed with the aid of a rotary
evaporator to provide the pure desired product (3).
Conclusion
We have developed a simple, general and efficient copper-
catalyzed method for the synthesis of aryl iodides, aryl
azides, aryl sulfones, phenols, arylamines, and nitroarenes
from arylboronic acids. The protocol uses very cheap Cu2O/
NH3 as the catalyst system, environmentally friendly water
as the solvent, oxygen in air as the oxidant, and the readily
available and cheap reagents (KI, NaN3, NaSO2R, NaOH,
NH3·H2O, and NaNO2) as the sources of the functional
groups, and the functionalizations of arylboronic acids were
performed well at room temperature. The target products
were easily extracted with ethyl acetate from aqueous solu-
tion and the remaining catalyst system in water could be re-
covered and reused. The method is of excellent tolerance to-
wards various functional groups in the substrates. To the
best of our knowledge, no general method exists for the as-
sembly of functional groups on aromatic rings thus far, so
the simple, general, environmentally friendly, and easy
workup approach will attract much attention in academic
and industrial fields.
General procedure for the synthesis of sulfones (4): A round-bottomed
flask was charged with a magnetic stirrer, Cu2O (0.1 mmol, 14.3 mg),
25% aqueous ammonia (0.19 mL, 2.5 mmol of NH3), and water (0.5 mL)
and the mixed solution was stirred for 30 min under air at room tempera-
ture (~258C). Arylboronic acid (1 mmol), RSO2Na (5 mmol, 510 mg for
R=CH3; 820 mg for R=Ph; 890 mg for R=PhCH3) and water (1.5 mL)
were added to the flask. The flask was not sealed in order that air could
enter the flask, and the mixture was allowed to stir for the shown time in
Table 2C under air at room temperature. After completion of the reac-
tion (the reaction progress was monitored by 1H NMR spectrsocopy),
aqueous NaOH (2n, 1.5 mL) was added to the resulting solution, and the
target product was extracted with ethyl acetate (3ꢁ2 mL). The combined
organic phase was dried over anhydrous MgSO4 and filtered and the sol-
vent of the filtrate was removed with the aid of a rotary evaporator to
provide the pure desired product (4; except for compounds 4a–c, 4g, and
4m–r). An extra purification by column chromatography on silica gel was
required for compounds 4a–c, 4g, and 4m–r.
General procedure for the synthesis of phenols (5): A round-bottomed
flask was charged with a magnetic stirrer, Cu2O (0.1 mmol, 14.3 mg),
25% aqueous ammonia (0.19 mL, 2.5 mmol of NH3), and water (0.5 mL),
and the mixed solution was stirred for 30 min under air at room tempera-
ture (~258C). Arylboronic acid (1 mmol), NaOH (3 mmol, 120 mg), and
water (1.5 mL) were added to the flask. The flask was not sealed in order
that air could enter the flask, and the mixture was allowed to stir for the
shown time in Table 2D under air at room temperature. After completion
of the reaction (the reaction progress was monitored by 1H NMR spec-
troscopy), HCl (1n, 2 mL) was added to acidify the solution (pH 2–3),
and the target product was extracted with ethyl acetate (3ꢁ2 mL). The
combined organic phase was dried over anhydrous MgSO4 and filtered,
and the solvent of the filtrate was removed with the aid of a rotary evap-
orator to provide the pure desired product (5).
Experimental Section
General methods: All reagents and solvents were obtained from commer-
cial suppliers and used without further purification. Cu2O was commer-
cially available from the Shanghai Qingong Wujiyan Company, and other
chemicals were purchased from Beijing Ouhe Technology Company and
Alfa Aesar Company. All reagents were weighed and handled in air at
room temperature. 1H and 13C NMR spectra were recorded by using tet-
ramethylsilane (TMS) in the solvent of CDCl3 as the internal standard
(1H NMR: TMS at d=0.00 ppm, CDCl3 at d=7.26 ppm; 13C NMR:
CDCl3 at d=77.0 ppm) or were recorded by using tetramethylsilane
(TMS) in the solvent of [D6]DMSO as the internal standard (1H NMR:
TMS at d=0.00 ppm, DMSO at d=2.50 ppm; 13C NMR: DMSO at d=
39.0 ppm).
General procedure for the synthesis of arylamines (6): A round-bottom
flask was charged with a magnetic stirrer, Cu2O (0.1 mmol, 14.3 mg),
25% aqueous ammonia (0.19 mL, 2.5 mmol of NH3), and water (0.5 mL),
and the mixed solution was stirred for 30 min under air at room tempera-
ture (~258C). Arylboronic acid (1 mmol), aqueous ammonia (6.5 mmol,
0.5 mL), and water (1.0 mL) were added to the flask. The flask was not
sealed in order that air could enter the flask and the mixture was allowed
to stir for the shown time in Table 3A under air at room temperature.
After completion of the reaction (the reaction progress was monitored
by 1H NMR spectroscopy), aqueous NaOH (2n, 1.5 mL) was added to
the resulting solution, and the target product was extracted with ethyl
acetate (3ꢁ2 mL). The combined organic phase was dried over anhy-
drous MgSO4 and filtered and the solvent of the filtrate was removed
with the aid of a rotary evaporator to provide the pure desired product
(6).
General procedure for the synthesis of aryl iodides (2): A round-bottom
flask was charged with a magnetic stirrer, Cu2O (0.1 mmol, 14.3 mg),
25% aqueous ammonia (0.19 mL, 2.5 mmol of NH3), and water (0.5 mL),
and the mixed solution was stirred for 30 min under air at room tempera-
ture (~258C). Arylboronic acid (1 mmol), KI (5 mmol, 830 mg), and
water (1.5 mL) were added to the flask. The flask was not sealed in order
that air could enter the flask, and the mixture was allowed to stir for
about 24 h under air at room temperature. Aqueous NaOH (2 N, 1.5 mL)
was added to the resulting solution (no addition of NaOH for compound
2i) and the target product was extracted with ethyl acetate (3ꢁ2 mL).
The combined organic phase was dried over anhydrous MgSO4 and fil-
tered and the solvent of the filtrate was removed with the aid of a rotary
evaporator to provide the pure desired product (2; except for compounds
2b and 2i). An extra purification by column chromatography on silica gel
was required for compounds 2b and 2i.
General procedure for the synthesis of nitroarenes (7): A round-bot-
tomed flask was charged with
a magnetic stirrer, Cu2O (0.1 mmol,
14.3 mg), 25% aqueous ammonia (0.14 mL, 1.8 mmol of NH3), and water
(0.5 mL), and the mixed solution was stirred for 30 min under air at
room temperature (~258C). Arylboronic acid (1 mmol), NaNO2 (7 mmol,
483 mg), and water (1.5 mL) were added to the flask. The flask was not
sealed in order that air could enter the flask, and the mixture was al-
lowed to stir for the shown time in Table 3B under air at room tempera-
ture. After completion of the reaction (the reaction progress was moni-
tored by 1H NMR spectroscopy) the target product was extracted with
ethyl acetate (3ꢁ2 mL). The combined organic phase was dried over an-
hydrous MgSO4 and filtered, the solvent of the filtrate was removed with
the aid of a rotary evaporator, and the residue was purified by column
chromatography on silica gel to provide the desired product (7).
General procedure for the synthesis of azides (3): A round-bottomed
flask was charged with a magnetic stirrer, Cu2O (0.1 mmol, 14.3 mg),
25% aqueous ammonia (0.19 mL, 2.5 mmol of NH3), and water (0.5 mL)
and the mixed solution was stirred for 30 min under air at room tempera-
ture (~258C). Arylboronic acid (1 mmol), NaN3 (5 mmol, 325 mg), and
water (1.5 mL) were added to the flask. The flask was not sealed in order
that air could enter the flask and the mixture was allowed to stir for the
shown time in Table 2B under air at room temperature. After completion
of the reaction (the reaction progress was monitored by 1H NMR spec-
troscopy), aqueous NaOH (2n, 1.5 mL) was added to the resulting solu-
tion and the target product was extracted with ethyl acetate (3ꢁ2 mL).
Reuse of the copper/ammonia catalyst system (Cu2O/NH3): Here, iodina-
tion of phenylboronic acid was chosen as
a model example (see
Scheme 1). The resulting solution was extracted with ethyl acetate (3ꢁ
2 mL) after the first iodination of phenylboronic acid under the standard
conditions and the copper/ammonia catalyst system in the remaining
Chem. Eur. J. 2011, 17, 5652 – 5660
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5655

H. Fu et al.
13C NMR (CDCl3, 150 MHz): d=137.5, 137.2, 131.2, 90.2 ppm; EIMS:
m/z: 218.0 [M]+.
4-Fluoroiodobenzene (2c):[25] Colorless oil; yield: 81% (180 mg);
1H NMR (CDCl3, 600 MHz): d=7.63 (m, 2H), 6.83 ppm (t, 2H, J=
8.2 Hz); 13C NMR (CDCl3, 150 MHz): d=162.7 (d, J=247.1 Hz), 138.9
(d, J=7.2 Hz), 117.8 (d, J=21.7 Hz), 86.9 ppm (d, J=2.9 Hz); EIMS: m/
z: 222.0 [M]+.
4-Iodobenzyl alcohol (2d):[27] White solid; yield: 93% (218 mg); m.p. 71–
738C; 1H NMR (CDCl3, 600 MHz): d=7.68 (d, 2H, J=8.3 Hz), 7.11 (d,
2H, J=8.3 Hz), 4.69 ppm (s, 2H); 13C NMR (CDCl3, 150 MHz): d=
140.5, 137.7, 129.0, 128.9, 93.1, 64.8 ppm; EIMS: m/z: 234.0 [M]+.
4-Iodobenzaldehyde (2e):[27] Yellow solid; yield: 82% (190 mg); m.p. 77–
788C; 1H NMR (CDCl3, 600 MHz): d=9.96 (s, 1H), 7.92 (d, 2H, J=
8.1 Hz), 7.59 ppm (d, 2H, 8.1 Hz); 13C NMR (CDCl3, 150 MHz): d=
191.5, 138.5, 138.5, 135.6, 130.9, 130.9, 102.9 ppm; EIMS: m/z:
232.0 [M]+.
Methyl 4-iodobenzoate (2 f):[28] White solid; yield: 80% (210 mg); m.p.
119–1208C; 1H NMR (CDCl3, 600 MHz): d=7.80 (d, 2H, J=8.2 Hz),
7.74 (d, 2H, J=8.2 Hz), 3.91 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz):
d=166.7, 137.8, 131.1, 129.7, 100.8, 52.4 ppm; EIMS: m/z: 262.0 [M]+.
Scheme 1. Reuse of the copper/ammonia catalyst system for the iodina-
tion of phenylboronic acid.
aqueous phase was reused in the following iodination of phenylboronic
acid. The organic phase was washed with aqueous NaOH (2n, 3ꢁ
1.5 mL), dried over anhydrous MgSO4, and concentrated to give iodoben-
zene in 82% yield (the first time). Then, phenylboronic acid (1 mmol),
KI (1 mmol), K2CO3 (1.5 mmol), and water (0.5 mL) were added to the
remaining aqueous phase with the copper/ammonia catalyst system
above (the addition of K2CO3 aimed at neutralizing the released boronic
acid from the first time). The second iodination was performed under the
same conditions and the target product was provided in 74% yield after
a similar workup procedure to the first cycle. Further, the third and
fourth cycles afforded 1-iodobenzene in the same yield (72%).
4-Iodophenyl methyl ether (2g):[26] Yellow liquid; yield: 78% (183 mg);
1H NMR (CDCl3, 600 MHz): d=7.27 (d, 1H, J=7.6 Hz), 7.24 (s, 1H),
6.98 (dd, 1H, J=7.6, 8.2 Hz), 6.85 (d, 1H, J=7.6, 8.2 Hz), 3.77 ppm (s,
3H); 13C NMR (CDCl3, 150 MHz): d=160.2, 130.9, 129.9, 123.1, 113.9,
94.5, 55.5 ppm; EIMS:
m/z: 234.0 [M]+.
1-Chloro-3-iodo-benzene (2h):[29] Colorless oil; yield: 86% (205 mg);
1H NMR (CDCl3, 600 MHz): d=7.72 (s, 1H), 7.59 (d, 1H, J=8.3 Hz),
7.32 (d, 1H, J=8.3 Hz), 7.03 ppm (t, 1H, J=8.3 Hz); 13C NMR (CDCl3,
150 MHz): d=137.2, 135.76, 135.1, 131.1, 128.1, 94.2 ppm; EIMS: m/z:
237.9 [M]+.
3-Iodobenzoic acid (2i):[30] Eluent: ethyl acetate/n-pentane 1:4; white
solid; yield: 70% (174 mg); m.p. 186–1898C; 1H NMR ([D6]DMSO,
600 MHz): d=13.23 (s, 1H), 8.23 (s, 1H), 7.98 (d, 1H, J=8.3 Hz), 7.94
(d, 1H, J=7.6 Hz), 7.31 ppm (dd, 1H, J=7.6, 8.3 Hz); 13C NMR
([D6]DMSO, 150 MHz): d=165.4, 140.8, 137.1, 132.3, 130.3, 128.0,
94.1 ppm; ESIMS: m/z: 249.0 [M+H]+.
The recyclable experimental procedures for the azidonation, sulfonyla-
tion, amination, and ipso-nitration of phenylboronic acid were similar to
ones for iodination of phenylboronic acid.
For hydroxylation of phenylboronic acid, the experimental details were
slightly different to the procedures above (see Scheme 2). After comple-
tion of the first coupling reaction, HCl (1n, 2 mL) was added to acidify
3-Iodonitrobenzene (2j):[29] Yellow solid; yield: 84% (209 mg); m.p. 35–
378C; 1H NMR (CDCl3, 600 MHz): d=8.56 (s, 1H), 8.21 (d, 1H, J=
8.3 Hz), 8.03 (d, 1H, J=8.3 Hz), 7.30 ppm (t, 1H, J=8.3 Hz); 13C NMR
(CDCl3, 150 MHz): d=148.6, 143.6, 132.51, 130.8, 122.8, 93.6 ppm;
EIMS: m/z: 249.0 [M]+.
2-Iodotoluene (2k):[26] Pale-yellow oil; yield: 81% (176 mg); 1H NMR
(CDCl3, 600 MHz): d=7.81 (d, 1H, J=7.6 Hz), 7.24 (d, 2H, J=4.1 Hz),
6.86 ppm (m, 1H); 13C NMR (CDCl3, 150 MHz): d=141.3, 138.9, 129.7,
128.1, 127.4, 101.1, 28.1 ppm; EIMS: m/z: 217.9 [M]+.
1-Bromo-2-iodo-benzene (2l):[25] Red oil; yield: 72% (204 mg); 1H NMR
(CDCl3, 600 MHz): d=7.83 (d, 1H, J=7.6 Hz), 7.61 (d, 1H, J=7.6 Hz),
7.20 (t, 1H, J=7.6 Hz), 6.98 ppm (t, 1H, J=7.6 Hz); 13C NMR (CDCl3,
150 MHz): d=140.4, 132.9, 129.8, 129.5, 128.5, 101.3 ppm; EIMS: m/z:
281.9, 283.9 [M]+.
2,5-Dichloroiodobenzene (2m):[31] Brown oil; yield: 81% (220 mg);
1H NMR (CDCl3, 600 MHz): d=7.84 (d, 1H, J=2.1 Hz), 7.35 (d, 1H, J=
8.3 Hz), 7.26 ppm (dd, 1H, J=2.1, 8.3 Hz); 13C NMR (CDCl3, 150 MHz):
d=139.5, 137.2, 132.9, 129.8, 129.6, 98.4 ppm; EIMS: m/z: 271.9 [M]+.
5-Iodo-2-methoxybenzaldehyde (2n):[32] Yellow solid; yield: 84%
(220 mg); m.p. 142–1438C; 1H NMR (CDCl3, 600 MHz): d=10.3 (s, 1H),
8.09 (d, 1H, J=2.0 Hz), 7.82 (dd, 1H, J=2.0, 8.9 Hz), 6.78 (d, 1H, J=
8.9 Hz), 3.92 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=188.4, 166.5,
144.2, 137.1, 126.6, 114.2, 83.1, 56.0 ppm; EIMS: m/z: 262.0 [M]+.
Scheme 2. Reuse of the copper/ammonia catalyst system for the hydrox-
ylation of phenylboronic acid.
the solution (pH 2–3), and the target product was extracted with ethyl
acetate (3ꢁ2 mL). The combined organic phase was dried over anhy-
drous MgSO4 and filtered and the solvent of the filtrate was removed
with the aid of a rotary evaporator to provide the phenol in 92% yield
(the first time). NH4Cl was added to the remaining aqueous solution till
pH 7 and then phenylboronic acid (1 mmol), NaOH (2 mmol), and water
(0.5 mL) were added to the solution. The second hydroxylation was per-
formed under the same conditions and the target product was provided
in 85% yield after a similar workup procedure to the first cycle. Further,
the third and fourth cycles provided the phenol in the same yield (82%).
Iodobenzene (2a):[25] Colorless oil; yield: 83% (169 mg); 1H NMR
(CDCl3, 600 MHz) d=7.69 (d, 2H, J=7.6 Hz), 7.32 (t, 1H, J=7.6 Hz),
7.09 ppm (t, 2H, J=7.6 Hz); 13C NMR (CDCl3, 150 MHz): d=137.4,
130.2, 127.4, 94.4 ppm; EIMS: m/z: 204.0 [M]+.
1-Iodonaphthalene (2o):[26] Dark-brown oil; yield: 85% (216 mg);
1H NMR (CDCl3, 600 MHz): d=8.08 (d, 2H, J=8.3 Hz), 7.84 (d, 1H,
8.3 Hz), 7.77 (d, 1H, J=8.3 Hz), 7.58 (t, 1H, J=8.3 Hz), 7.52 (t, 1H, J=
8.3 Hz), 7.18 ppm (t, 1H, J=8.3 Hz); 13C NMR (CDCl3, 150 MHz): d=
137.5, 134.5, 134.2, 132.2, 129.1, 128.7, 127.8, 126.9, 126.8, 99.7 ppm;
EIMS: m/z: 254.0 [M]+.
4-Iodotoluene (2b):[26] Eluent: ethyl acetate/n-pentane (1:7); yellow
solid; yield: 83% (181 mg); m.p. 34–358C; 1H NMR (CDCl3, 600 MHz):
d=7.55 (d, 2H, J=4.1 Hz), 6.91 (d, 2H, J=4.1 Hz), 2.27 ppm (s, 3H);
5656
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5652 – 5660

Copper-Catalyzed Transformations
FULL PAPER
2-Iodonaphthalene (2p):[30] White solid; yield: 86% (218 mg); m.p. 53–
558C; H NMR (CDCl3, 600 MHz): d=8.23 (s, 1H), 7.77 (dd, 1H, J=3.5,
6.2 Hz), 7.70 (m, 2H), 7.55 (d, 1H, J=8.9 Hz), 7.47 ppm (dd, 2H, J=3.5,
6.2 Hz); 13C NMR (CDCl3, 150 MHz): d=136.7, 135.1, 134.5, 132.2, 129.6,
127.9, 126.9, 126.6, 125.89, 91.5 ppm; EIMS: m/z: 254.0 [M]+.
5-Azido-2-methoxybenzaldehyde (3l): Brown solid; yield: 85% (150 mg);
m.p. 86–888C; 1H NMR (CDCl3, 600 MHz): d=10.44 (s, 1H), 7.53 (s,
1H), 7.18 (d, 1H, J=8.9 Hz), 6.99 (d, 1H, J=8.9 Hz), 3.93 ppm (s, 3H);
13C NMR (CDCl3, 150 MHz): d=188.7, 159.1, 133.2, 126.4, 125.5, 118.0,
113.3, 56.1 ppm; EIMS: m/z: 177.1 [M]+.
1
1-Azidonaphthalene (3m):[17b] Black oil; yield: 80% (135 mg); 1H NMR
(CDCl3, 600 MHz): d=8.02 (d, 1H, J=7.6 Hz), 7.74 (d, 1H, J=7.6 Hz),
7.55 (d, 1H, J=8.3 Hz), 7.43 (m, 2H), 7.38 (t, 1H, J=7.6 Hz), 7.18 ppm
(d, 1H, J=7.6 Hz); 13C NMR (CDCl3, 150 MHz): d=136.5, 134.3, 127.7,
126.8, 126.1, 125.6, 124.7, 122.5, 113.9 ppm; EIMS: m/z: 168.9 [M]+.
2-Azidonaphthalene (3n):[38] Black oil; yield: 77% (130 mg); 1H NMR
(CDCl3, 600 MHz): d=7.83 (d, 1H, J=8.3 Hz), 7.81 (d, 1H, J=8.3 Hz),
7.76 (d, 1H, J=8.3 Hz), 7.49 (t, 1H, J=8.3 Hz), 7.45 (s, 1H), 7.43 (t, 1H,
J=7.6 Hz), 7.16 ppm (d, 1H, J=8.3 Hz); 13C NMR (CDCl3, 150 MHz):
d=137.5, 134.0, 131.0, 129.9, 127.8, 127.0, 125.4, 118.7, 115.8 ppm; EIMS:
m/z: 169.1 [M]+.
4-Iododibenzofuran (2q):[33] Purple solid; yield: 76% (223 mg); m.p. 47–
498C; 1H NMR (CDCl3, 600 MHz): d=7.91 (d, 1H, J=8.2 Hz), 7.89 (d,
1H, J=7.6 Hz), 7.80 (d, 1H, J=8.2 Hz), 7.65 (d, 1H, J=8.2 Hz), 7.48
(dd, 1H, J=8.2, 7.6 Hz), 7.36 (dd, 1H, J=8.2, 7.6 Hz), 7.09 ppm (dd, 1H,
J=7.6 Hz, 8.2 Hz); 13C NMR (CDCl3, 150 MHz): d=156.4, 155.7, 135.9,
127.7, 124.6, 124.5, 124.4, 123.2, 121.1, 120.5, 112.1, 75.4 ppm; EIMS: m/z:
294.0 [M]+.
(E)-(2-Iodovinyl)benzene (2r):[34] Colorless oil; yield: 80% (184 mg);
1H NMR (CDCl3, 600 MHz): d=7.42 (d, 1H, J=15.1 Hz), 7.30 (m, 5H),
6.81 ppm (d, 1H, J=15.1 Hz); 13C NMR (CDCl3, 150 MHz): d=145.1,
137.8, 128.8, 128.5, 126.1, 76.7 ppm; EIMS: m/z: 229.9 [M]+.
(E)-(2-Azidovinyl)benzene (3o):[9] Black oil; yield: 84% (122 mg);
1H NMR (CDCl3, 600 MHz): d=7.31–7.17 (m, 5H), 6.57 (d, 1H, J=
13.8 Hz), 6.25 ppm (d, 1H, J=13.8 Hz); 13C NMR (CDCl3, 150 MHz):
d=135.0, 128.7, 127.3, 126.6, 125.8, 119.7 ppm; EIMS: m/z: 145.0 [M]+.
1
Azidobenzene (3a):[9] Yellow oil; yield: 87% (104 mg); H NMR (CDCl3,
600 MHz): d=7.35 (t, 2H, J=7.6 Hz), 7.14 (t, 1H, J=7.6 Hz), 7.03 ppm
(d, 2H, J=7.6 Hz); 13C NMR (CDCl3, 150 MHz): d=140.0, 129.7, 124.9,
119.0 ppm; EIMS: m/z: 119.0 [M]+.
1-Methyl-4-(methylsulfonyl)benzene (4a):[39] Eluent: ethyl acetate/petro-
leum ether (1:10); yellow solid; m.p. 84–868C; yield: 74% (126 mg);
1H NMR (CDCl3, 600 MHz): d=7.83 (d, 2H, J=8.3 Hz), 7.37 (d, 2H, J=
8.3 Hz), 3.04 (s, 3H), 2.46 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=
144.6, 137.7, 129.9, 127.3, 44.6, 21.6 ppm; EIMS: m/z: 170.1 [M]+.
1-Methoxy-4-(methylsulfonyl)benzene (4b):[18] Eluent: ethyl acetate/pe-
troleum ether (1:10); brown solid; m.p. 110–1138C; yield: 76% (139 mg);
1H NMR (CDCl3, 600 MHz): d=7.88 (d, 2H, J=8.9 Hz), 7.03 (d, 2H, J=
8.9 Hz), 3.89 (s, 3H), 3.03 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=
163.7, 132.3, 129.5, 114.5, 55.7, 44.8 ppm; EIMS: m/z: 186.0.
1-Methoxy-3-(methylsulfonyl)benzene (4c):[40] Eluent: ethyl acetate/pe-
troleum ether (1:10); black oil; yield: 70% ( 130 mg); 1H NMR (CDCl3,
600 MHz): d=7.53 (d, 1H, J=7.6 Hz), 7.48 (t, 1H, J=7.6 Hz), 7.44 (s,
1H), 7.17 (d, 1H, J=7.6 Hz), 3.88 (s, 3H), 3.06 ppm (s, 3H); 13C NMR
(CDCl3, 150 MHz): d=160.1, 141.7, 130.5, 120.1, 119.4, 111.8, 55.7,
44.4 ppm; EIMS: m/z: 186.1 [M]+.
(E)-[2-(Methylsulfonyl)vinyl]benzene (4d):[18] Black solid; m.p. 75–778C;
yield: 76% (176 mg); 1H NMR (CDCl3, 600 MHz): d=7.63 (d, 1H, J=
15.8 Hz), 7.52 (d, 2H, J=6.2 Hz), 7.44 (m, 3H), 6.92 (d, 1H, J=15.8 Hz),
3.04 ppm (s, 3H); 13C NMR (CDCl3, 75 MHz): d=144.0, 131.4, 129.2,
128.6, 126.2, 43.3 ppm; EIMS: m/z: 182.0 [M]+.
Sulfonyldibenzene (4e):[41] White solid; m.p. 125–1268C; yield: 76%
(166 mg); 1H NMR (CDCl3, 600 MHz): d=7.95 (d, 4H, J=7.6 Hz), 7.56
(t, 2H, J=7.6 Hz), 7.50 ppm (t, 4H, J=7.6 Hz); 13C NMR (CDCl3,
150 MHz): d=141.7, 133.3, 129.4, 127.8 ppm; EIMS: m/z: 218.0 [M]+.
1-Methyl-4-(phenylsulfonyl)benzene (4 f):[41] White solid; m.p. 126–
1278C; yield: 81% (188 mg); 1H NMR (CDCl3, 600 MHz): d=7.93 (d,
2H, J=8.2 Hz), 7.82 (d, 2H, J=8.2 Hz), 7.53 (t, 1H, J=7.6 Hz), 7.49 (t,
2H, J=7.6 Hz), 7.29 (d, 2H, J=8.2 Hz), 2.39 ppm (s, 3H); 13C NMR
(CDCl3, 150 MHz): d=144.1, 142.0, 138.6, 132.9, 129.9, 129.2, 127.7,
127.5, 21.5 ppm; EIMS: m/z: 232.0 [M]+.
Methyl 4-(phenylsulfonyl)benzoate (4g):[41] Eluent: ethyl acetate/petrole-
um ether (1:10); yellow solid; m.p. 142–1458C; yield: 82% (226 mg);
1H NMR (CDCl3, 600 MHz): d=8.15 (d, 2H, J=7.6 Hz), 8.01 (d, 2H, J=
7.6 Hz), 7.95 (d, 2H, J=7.6 Hz), 7.60 (d, 1H, J=6.9 Hz), 7.53 (m, 2H),
3.94 ppm (s, 3H); 13C NMR (CDCl3, 75 MHz): d=165.5, 145.5, 140.8,
134.3, 133.6, 130.4, 129.4, 127.9, 127.7, 52.7 ppm; EIMS: m/z: 276.0 [M]+.
1-Fluoro-4-(phenylsulfonyl)benzene (4h):[39] White solid; m.p. 105–
1078C; yield: 60% (142 mg); 1H NMR (CDCl3, 600 MHz): d=7.95 (m,
4H), 7.58 (t, 1H, J=7.6 Hz), 7.51 (t, 2H, J=7.6 Hz), 7.18 ppm (m, 2H);
13C NMR (CDCl3, 75 MHz): d=165.4 (d, J=258.6 Hz), 141.5, 137.7,
133.3, 130.5 (d, J=10.1 Hz), 129.4, 127.6, 116.6 ppm (d, J=23.1 Hz);
EIMS: m/z 236.0 [M]+.
1-Azido-4-methylbenzene (3b):[9] Brown oil; yield: 91% (121 mg);
1H NMR (CDCl3, 600 MHz): d=7.14 (d, 2H, J=8.3 Hz), 6.92 (d, 2H, J=
8.3 Hz), 2.32 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=137.1, 134.5,
130.2, 118.8, 20.7 ppm; EIMS: m/z: 133.0 [M]+;
1-Azido-4-methoxybenzene (3c):[9] Black oil; yield: 92% (137 mg);
1H NMR (CDCl3, 600 MHz): d=6.95 (d, 2H, J=8.9 Hz), 6.88 (d, 2H, J=
8.9 Hz), 3.79 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=157.0, 132.4,
120.0, 115.1, 55.6 ppm; EIMS: m/z: 149.1 [M]+.
1
4-Azidobenzaldehyde (3d):[35] Yellow oil; yield: 79% (116 mg); H NMR
(CDCl3, 300 MHz): d=9.95 (s, 1H), 7.89 (d, 2H, J=8.3 Hz), 7.16 ppm (d,
2H, J=8.3 Hz); 13C NMR (CDCl3, 150 MHz): d=190.6, 146.3, 133.2,
131.5, 119.5 ppm; EIMS: m/z: 147.0 [M]+.
Methyl 4-azidobenzoate (3e):[9] Yellow oil; yield: 89% (157 mg);
1H NMR (CDCl3, 600 MHz): d=8.02 (d, 2H, J=8.3 Hz), 7.05 (d, 2H, J=
8.3 Hz), 3.90 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=166.2, 144.7,
131.3, 126.6, 118.7, 52.0 ppm; EIMS: m/z: 177.1 [M]+.
1-Azido-3-methoxybenzene (3 f):[9] Black oil; yield: 86% (128 mg);
1H NMR (CDCl3, 600 MHz): d=7.25 (t, 1H, J=8.3 Hz), 6.69 (d, 1H, J=
8.3 Hz), 6.64 (d, 1H, J=8.3 Hz), 6.55 (s, 1H), 3.80 ppm (s, 3H);
13C NMR (CDCl3, 150 MHz): d=160.8, 141.3, 130.4, 111.3, 110.7, 104.9,
55.4 ppm; EIMS: m/z: 149.0 [M]+.
1-Azido-3-chlorobenzene (3g):[9] Brown oil; yield: 70% (107 mg);
1H NMR (CDCl3, 600 MHz): d=7.25 (dd, 1H, J=7.6, 8.3 Hz), 7.10 (d,
1H, J=7.6 Hz), 7.00 (s, 1H), 6.90 ppm (d, 1H, J=8.3 Hz); 13C NMR
(CDCl3, 150 MHz): d=141.4, 135.4, 130.6, 125.0, 119.3, 117.2 ppm;
EIMS: m/z: 153.0 [M]+.
1-Azido-3-benzyl alcohol (3h):[36] Brown oil; yield: 82% (122 mg);
1H NMR (CDCl3, 600 MHz): d=7.33 (dd, 1H, J=8.3, 7.6 Hz), 7.11 (d,
1H, J=7.6 Hz), 7.04 (s, 1H), 6.94 (d, 1H, J=8.3 Hz), 4.67 ppm (s, 2H);
13C NMR (CDCl3, 150 MHz): d=142.9, 140.3, 129.9, 123.2, 118.2, 117.3,
64.7 ppm; EIMS: m/z: 149.1 [M]+.
1
1-Azido-3-nitrobenzene (3i):[9] Yellow oil; yield: 80% (131 mg); H NMR
(CDCl3, 600 MHz): d=8.00 (d, 1H, J=8.3 Hz), 7.89 (s, 1H), 7.54 (t, 1H,
J=8.3 Hz), 7.34 ppm (d, 1H, J=8.3 Hz); 13C NMR (CDCl3, 150 MHz):
d=149.2, 141.9, 130.5, 124.8, 119.6, 114.0 ppm; EIMS: m/z: 164.0 [M]+.
1-Azido-2-bromobenzene (3j):[37] Brown oil; yield: 60% (118 mg);
1H NMR (CDCl3, 600 MHz): d=7.55 (d, 1H, J=8.2 Hz), 7.34 (t, 1H, J=
7.6 Hz), 7.17 (d, 1H, J=8.2 Hz), 7.00 ppm (t, 1H, J=7.6 Hz); 13C NMR
(CDCl3, 150 MHz): d=138.6, 133.8, 128.5, 125.9, 119.4, 113.8 ppm;
EIMS: m/z: 196.9, 198.9 [M]+.
2-Azido-1,4-dichlorobenzene (3k):[35] Yellow oil; yield: 72% (135 mg);
1H NMR (CDCl3, 600 MHz): d=7.29 (d, 1H, J=8.6 Hz), 7.15 (d, 1H, J=
2.4 Hz), 7.05 ppm (dd, 1H, J=8.6, 2.4 Hz); 13C NMR (CDCl3, 150 MHz):
d=138.4, 133.4, 131.5, 125.7, 123.4, 119.8 ppm; EIMS: m/z 187.0, 189.0,
191.0 [M]+.
1-Chloro-3-(phenylsulfonyl)benzene (4i): Yellow solid; m.p. 100–1018C;
1
yield: 70% (176 mg); H NMR (CDCl3, 600 MHz): d=7.94 (m, 3H), 7.83
(d, 1H, J=7.6 Hz), 7.60 (t, 1H, J=7.6 Hz), 7.53 (m, 3H), 7.45 ppm (t,
Chem. Eur. J. 2011, 17, 5652 – 5660
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5657

H. Fu et al.
1H, J=8.3 Hz); 13C NMR (CDCl3, 150 MHz): d=143.4, 140.9, 135.5,
133.6, 133.3, 130.6, 129.4, 127.4, 127.8, 127.7, 125.8 ppm; EIMS: m/z:
252.0 [M]+.
8.3 Hz), 4.60 (s, 1H), 2.27 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=
153.2, 130.1, 130.0, 115.0, 20.4 ppm; EIMS: m/z: 108.1 [M]+.
4-Methoxyphenol (5c):[19] Colorless solid; m.p. 54–568C; yield: 94%
(117 mg); 1H NMR (CDCl3, 600 MHz): d=6.77 (m, 4H), 4.82 (s, 1H),
3.75 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=153.7, 149.4, 116.0,
114.8, 55.8 ppm; EIMS: m/z: 124.1 [M]+.
4-Hydroxybenzaldehyde (5d):[19] Red solid; m.p. 113–1158C; yield: 78%
(95 mg); 1H NMR (CDCl3, 600 MHz): d=9.88 (s, 1H), 7.81 (d, 2H, J=
8.3 Hz), 6.95 (d, 2H, J=8.3 Hz), 5.41 ppm (s, 1H); 13C NMR (CDCl3,
150 MHz): d=191.4, 161.9, 132.6, 129.6, 116.0 ppm; ESIMS: m/z: 121.5
[MÀH]À.
4-Hydroxybenzoic acid (5e): White solid; m.p. 213–2158C; yield: 75%
(104 mg); 1H NMR (CDCl3, 600 MHz): d=10.2 (s, 1H), 7.78 (d, 2H, J=
8.3 Hz), 6.82 ppm (d, 2H, J=8.3 Hz); 13C NMR (CDCl3, 150 MHz): d=
167.7, 162.1, 132.0, 121.9, 115.6 ppm; ESIMS: m/z: 137.3 [MÀH]+.
1-Nitro-3-(phenylsulfonyl)benzene (4j): Yellow solid; m.p. 77–788C;
yield: 62% (163 mg); 1H NMR (CDCl3, 600 MHz): d=8.77 (s, 1H), 8.42
(d, 1H, J=8.2 Hz), 8.27 (d, 1H, J=7.6 Hz), 7.99 (d, 2H, J=8.2 Hz), 7.74
(t, 1H, J=8.2 Hz), 7.63 (t, 1H, J=7.6 Hz), 7.57 ppm (t, 2H, J=7.6 Hz);
13C NMR (CDCl3, 75 MHz): d=148.4, 144.0, 140.1, 134.1, 133.1, 130.7,
129.7, 128.0, 127.7, 122.9 ppm; EIMS: m/z: 263.0 [M]+.
4,4’-Sulfonylbis(methylbenzene) (4k):[41] White solid; m.p. 158–1608C;
yield: 84% (207 mg); 1H NMR (CDCl3, 300 MHz): d=7.79 (d, 4H, J=
7.9 Hz), 7.25 (d, 4H, J=7.9 Hz), 2.36 ppm (s, 6H); 13C NMR (CDCl3,
75 MHz): d=143.9, 139.0, 129.8, 127.5, 21.4 ppm; EIMS: m/z:
246.1 [M]+.
1-Methoxy-4-tosylbenzene (4l):[41] Yellow solid; m.p. 100–1028C; yield:
80% (209 mg); 1H NMR (CDCl3, 600 MHz): d=7.85 (d, 2H, J=7.6 Hz),
7.79 (d, 2H, J=8.2 Hz), 7.26 (d, 2H, J=7.6 Hz), 6.94 (d, 2H, J=8.2 Hz),
3.82 (s, 3H), 2.37 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=163.2,
143.7, 139.3, 133.4, 129.8, 129.6, 127.3, 114.4, 55.6, 21.4 ppm; EIMS: m/z:
262.0 [M]+.
1-Fluoro-4-tosylbenzene (4m):[10] Eluent: ethyl acetate/petroleum ether
(1:20); brown solid; m.p. 83–858C; yield: 70% (175 mg); 1H NMR
(CDCl3, 600 MHz): d=7.94 (m, 2H), 7.81 (d, 2H, J=8.3 Hz), 7.30 (d,
2H, J=7.6 Hz), 7.16 (dd, 2H, J=8.3, 8.9 Hz), 2.40 ppm (s, 3H);
13C NMR (CDCl3, 150 MHz): d=165.3 (d, J=249.3 Hz), 144.3, 138.5,
138.1, 130.3 (d, J=9.4 Hz), 130.2, 130.0, 127.6, 116.5 (d, J=22.4 Hz),
21.5 ppm: EIMS: m/z: 250.0 [M]+.
Methyl 4-hydroxybenzoate (5 f): White solid; m.p. 123–1258C; yield:
86% (131 mg); 1H NMR (CDCl3, 600 MHz): d=7.96 (d, 2H, J=8.3 Hz),
6.86 (d, 2H, J=8.3 Hz), 5.43 (s, 1H), 3.89 ppm (s, 3H); 13C NMR
(CDCl3, 150 MHz): d=167.5, 160.3, 131.9, 122.2, 115.3, 52.1 ppm;
ESIMS: m/z: 151.6 [MÀH]+.
4-Hydroxybenzonitrile (5g):[43] Yellow solid; m.p. 94–958C; yield: 75%
(79 mg); 1H NMR (CDCl3, 600 MHz): d=7.55 (d, 2H, J=8.3 Hz), 6.94
(d, 2H, J=8.3 Hz), 6.72 ppm (s, 1H); 13C NMR (CDCl3, 150 MHz): d=
160.2, 134.3, 119.2, 116.4, 102.9 ppm; EIMS: m/z: 119.1 [M]+.
1
o-Cresol (5h):[42] Pink solid; m.p. 30–318C; yield: 81% (88 mg); H NMR
(CDCl3, 600 MHz): d=7.11 (d, 1H, J=6.9 Hz), 7.07 (dd, 1H, J=8.3,
7.6 Hz), 6.84 (dd, 1H, J=7.6, 6.9 Hz), 6.75 (d, 1H, J=8.3 Hz), 4.97 (s,
1H), 2.24 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=153.7, 131.0,
127.1, 123.8, 120.7, 114.9, 15.7 ppm; EIMS: m/z: 108.1 [M]+.
2-Bromophenol (5i): Colorless oil; yield: 90% (156 mg); 1H NMR
(CDCl3, 600 MHz): d=7.45 (d, 1H, J=8.3 Hz), 7.21 (dd, 1H, J=7.6 Hz,
8.3 Hz), 7.02 (d, 1H, J=8.3 Hz), 6.80 (d, 1H, J=7.6 Hz), 5.52 ppm (s,
1H); 13C NMR (CDCl3, 150 MHz): d=152.2, 132.0, 129.1, 121.8, 116.1,
110.2 ppm; EIMS: m/z: 172.0, 174.0 [M]+.
1-Tosyl-4-(trifluoromethyl)benzene (4n):[39] Eluent: ethyl acetate/petrole-
um ether (1:10); yellow solid; m.p. 105–1078C; yield: 70% (210 mg);
1H NMR (CDCl3, 600 MHz): d=8.05 (d, 2H, J=8.2 Hz), 7.84 (d, 2H, J=
8.2 Hz), 7.75 (d, 2H, J=8.2 Hz), 7.33 (d, 2H, J=8.2 Hz), 2.41 ppm (s,
3H); 13C NMR (CDCl3, 150 MHz): d=145.6, 144.9, 137.6, 134.6 (q, J=
30.3 Hz), 130.2, 128.0, 127.9, 126.4 (q, J=2.9 Hz), 123.1 (q, J=273.1 Hz),
21.6 ppm; EIMS: m/z: 300.0 [M]+.
4-Tosylbenzaldehyde (4o):[10] Eluent: ethyl acetate/petroleum ether (1:5);
yellow solid; m.p. 142–1448C; yield: 70% (182 mg); 1H NMR (CDCl3,
300 MHz): d=10.1 (s,1H), 8.09 (d, 2H, J=8.6 Hz), 7.98 (d, 2H, J=
7.9 Hz), 7.85 (d, 2H, J=8.3 Hz), 7.33 (d, 2H, J=7.9 Hz), 2.41 ppm (s,
3H); 13C NMR (CDCl3, 75 MHz): d=190.7, 147.1, 144.9, 139.0, 137.5,
130.2, 130.1, 128.1, 128.0, 21.6 ppm; EIMS: m/z: 260.1 [M]+.
4-Tosylbenzonitrile (4p):[10] Eluent: ethyl acetate/petroleum ether (1:10);
yellow solid; m.p. 129–1318C; yield: 60% (154 mg); 1H NMR (CDCl3,
300 MHz): d=8.03 (d, 2H, J=8.6 Hz), 7.83 (d, 2H, J=8.6 Hz), 7.78 (d,
2H, J=8.3 Hz), 7.34 (d, 2H, J=8.3 Hz), 2.42 ppm (s, 3H); 13C NMR
(CDCl3, 75 MHz): d=146.2, 145.2, 137.1, 133.0, 130.3, 128.1, 128.0, 117.2,
116.7, 21.6 ppm; EIMS: m/z: 257.1 [M]+.
1-Methoxy-3-tosylbenzene (4q):[10] Eluent: ethyl acetate/petroleum ether
(1:10); yellow solid; m.p. 65–678C; yield: 70% (183 mg); 1H NMR
(CDCl3, 600 MHz): d=7.82 (d, 2H, J=8.2 Hz), 7.49 (d, 1H, J=7.6 Hz),
7.44 (s, 1H), 7.38 (t, 1H, J=7.6 Hz), 7.29 (d, 2H, J=8.2 Hz), 7.05 (dd,
1H, J=2.0, 8.2 Hz), 3.83 (s, 3H), 2.39 ppm (s, 3H); 13C NMR (CDCl3,
75 MHz): d=160.0, 144.1, 143.1, 138.6, 130.3, 129.9, 127.7, 119.7, 119.3,
112.1, 55.6, 21.5 ppm; EIMS: m/z: 262.0 [M]+.
1-Tosyl-3-(trifluoromethyl)benzene (4r):[10] Eluent: ethyl acetate/petrole-
um ether (1:10); yellow solid; m.p. 81–838C; yield: 68% (204 mg);
1H NMR (CDCl3, 600 MHz): d=8.20 (s, 1H), 8.11 (d, 1H, J=7.6 Hz),
7.84 (d, 2H, J=8.2 Hz), 7.80 (d, 1H, J=8.2 Hz), 7.64 (t, 1H, J=7.6 Hz),
7.33 (d, 2H, J=7.6 Hz), 2.41 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz):
d=144.9, 143.4, 130.8, 130.2, 130.0, 129.8, 129.7, 127.9, 127.5, 124.5,
21.6 ppm; EIMS: m/z: 300.1 [M]+.
3-Methoxyphenol (5j):[19] Yellow oil; yield: 89% (110 mg); 1H NMR
(CDCl3, 600 MHz): d=7.13 (t, 1H, J=8.3 Hz), 6.50 (dd, 1H, J=2.1,
8.3 Hz), 6.43 (m, 2H), 4.80 (s, 1H), 3.78 ppm (s, 3H); 13C NMR (CDCl3,
150 MHz): d=161.0, 156.7, 130.1, 107.7, 106.4, 101.5, 55.3 ppm; EIMS:
m/z:124.0 [M]+.
5-Hydroxy-2-methoxybenzaldehyde (5k): Yellow solid; m.p. 111–1138C;
yield: 79% (120 mg); 1H NMR (CDCl3, 600 MHz): d=10.4 (s, 1H), 7.36
(d, 1H, J=2.8 Hz), 7.12 (dd, 1H, J=2.8, 8.9 Hz), 6.91 (d, 1H, J=8.9 Hz),
5.73 (s, 1H), 3.88 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=190.1,
156.6, 149.8, 125.0, 123.6, 113.7, 113.4, 56.1 ppm; ESIMS: m/z: 151.5
[MÀH]À.
Naphthalen-1-ol (5l):[42] Colorless solid; m.p. 109–1128C; yield: 82%
(118 mg); 1H NMR (CDCl3, 600 MHz): d=8.17 (m, 1H), 7.81 (m, 1H),
7.48 (m, 2H), 7.44 (d, 1H, J=8.3 Hz), 7.29 (dd, 1H, J=7.6, 8.3 Hz), 6.80
(d, 1H, J=7.6 Hz), 5.26 ppm (s, 1H); 13C NMR (CDCl3, 150 MHz): d=
151.3, 134.7, 127.6, 126.4, 125.8, 125.2, 124.3, 121.5, 120.7, 108.6 ppm;
EIMS: m/z 144.1 [M]+.
Naphthalen-2-ol (5m):[19] Pink solid; m.p. 123–1258C; yield: 80%
(115 mg); 1H NMR (CDCl3, 600 MHz): d=7.75 (dd, 2H, J=7.6, 8.9 Hz),
7.67 (d, 1H, J=8.3 Hz), 7.42 (dd, 1H, J=6.9, 8.3 Hz), 7.32 (dd, 1H, J=
6.9, 7.6 Hz), 7.14 (d, 1H, J=2.8 Hz), 7.09 (dd, 1H, J=2.8, 8.9 Hz),
4.99 ppm (s, 1H); 13C NMR (CDCl3, 150 MHz): d=153.2, 134.5, 129.8,
128.9, 127.7, 126.5, 126.3, 123.6, 117.7, 109.5 ppm; EIMS: m/z:
144.1 [M]+.
Aniline (6a):[20] Colorless oil; yield: 86% (80 mg); 1H NMR (CDCl3,
600 MHz): d=7.15 (t, 2H, J=7.6 Hz), 6.76 (t, 1H, J=7.6 Hz), 6.68 (d,
2H, J=7.6 Hz), 3.63 ppm (s, 2H); 13C NMR (CDCl3, 150 MHz): d=
146.5, 129.2, 118.5, 115.1 ppm; EIMS: m/z: 93.1 [M]+.
Phenol (5a):[19,42] Colorless solid; m.p. 38–408C; yield: 95% (89 mg);
1H NMR (CDCl3, 600 MHz): d=7.24 (t, 2H, J=7.6 Hz), 6.93 (t, 1H, J=
7.6 Hz), 6.83 ppm (d, 2H, J=7.6 Hz); 13C NMR (CDCl3, 150 MHz): d=
155.4, 129.7, 120.8, 115.3 ppm; EIMS: m/z: 94.1 [M]+.
p-Toluidine (6b):[20] Red solid; m.p. 44–458C; yield: 88% (93 mg);
1H NMR (CDCl3, 600 MHz): d=6.97 (d, 2H, J=8.3 Hz), 6.61 (d, 2H, J=
8.3 Hz), 3.51 (s, 2H), 2.24 ppm (s, 3H). 13C NMR (CDCl3, 150 MHz): d=
143.6, 129.7,127.8, 115.3, 20.4 ppm; EIMS: m/z: 106.1 [M]+.
p-Cresol (5b):[43] Colorless solid; m.p. 33–348C; yield: 95% (103 mg);
1H NMR (CDCl3, 600 MHz): d=7.03 (d, 2H, J=8.3 Hz), 6.72 (d, 2H, J=
5658
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5652 – 5660

Copper-Catalyzed Transformations
FULL PAPER
4-Methoxyaniline (6c):[12b] Red solid; m.p. 56–588C; yield: 88%
(108 mg); 1H NMR (CDCl3, 600 MHz): d=6.75 (d, 2H, J=8.9 Hz), 6.65
(d, 2H, J=8.9 Hz), 3.75 (s, 3H), 3.42 ppm (s, 2H); 13C NMR (CDCl3,
150 MHz): d=152.7, 139.9, 116.4, 114.7, 55.7 ppm; EIMS: m/z: 123.1
[M]+.
(s, 3H); 13C NMR (CDCl3, 150 MHz): d=146.1, 145.9, 129.8, 123.5,
21.6 ppm; EIMS: m/z: 137.0 [M]+.
4-Fluoronitrobenzene (7c):[21a] Eluent: ethyl acetate/petroleum ether
(1:20); yellow oil, yield: 52% (73 mg); 1H NMR (CDCl3, 600 MHz): d=
8.28 (m, 2H), 7.22 ppm (m, 2H); 13C NMR (CDCl3, 150 MHz): d=167.1,
165.4, 144.4, 126.3, 126.2, 116.5, 116.3 ppm; EIMS: m/z 141.0 [M]+.
4-Nitrobenzenemethanol (7d):[45] Eluent: ethyl acetate/petroleum ether
(1:10); yellow solid; m.p. 89–908C; yield: 70% (107 mg); 1H NMR
(CDCl3, 600 MHz): d=8.21 (d, 2H, J=8.3 Hz), 7.53 (d, 2H, J=8.3 Hz),
4.84 (d, 2H, J=4.8 Hz), 2.20 ppm (t, 1H, J=4.8 Hz); 13C NMR (CDCl3,
150 MHz): d=148.2, 147.2, 127.0, 123.7, 63.9 ppm; EIMS: m/z: 153.0
[M]+.
4-Nitrobenzaldehyde (7e):[45] Eluent: ethyl acetate/petroleum ether
(1:10); white solid; m.p. 103–1058C; yield: 50% (76 mg); 1H NMR
(CDCl3, 600 MHz): d=10.17 (s, 1H), 8.40 (d, 2H, J=8.3 Hz), 8.08 ppm
(d, 2H, J=8.3 Hz); 13C NMR (CDCl3, 150 MHz): d=190.3, 151.1, 140.0,
130.5, 124.3 ppm; EIMS: m/z: 151.0 [M]+.
4-(Trifluoromethyl)aniline (6d): Yellow oil; yield: 70% (113 mg);
1H NMR (CDCl3, 600 MHz): d=7.38 (d, 2H, J=8.3 Hz), 6.67 (d, 2H, J=
8.3 Hz), 3.90 ppm (s, 2H); 13C NMR (CDCl3, 150 MHz): d=149.3, 126.7
(d, J=2.9 Hz), 124.8 (d, J=271.7 Hz), 120.2 (d, J=33.2 Hz), 114.2 ppm;
EIMS: m/z: 161.1 [M]+.
(4-Aminophenyl)methanol (6e):[20] Colorless solid; m.p. 60–638C; yield:
82% (102 mg); 1H NMR (CDCl3, 600 MHz): d=7.16 (d, 2H, J=8.3 Hz),
6.67 (d, 2H, J=8.3 Hz), 4.55 (s, 2H), 3.68 ppm (s, 2H); 13C NMR
(CDCl3, 150 MHz): d=146.0, 131.0, 128.8, 115.1, 65.3 ppm; ESIMS: m/z:
124.2 [M+H]+.
Methyl 4-aminobenzoate (6 f):[20] White solid; m.p. 112–1138C; yield:
71% (107 mg); 1H NMR (CDCl3, 600 MHz): d=7.84 (d, 2H, J=8.9 Hz),
6.63 (d, 2H, J=8.9 Hz), 4.10 (s, 2H), 3.85 ppm (s, 3H); 13C NMR
(CDCl3, 150 MHz): d=167.1, 150.8, 131.5, 119.6, 113.7, 51.5 ppm; EIMS:
m/z: 151.1 [M]+.
4-Aminobenzonitrile (6g):[20] Yellow solid; m.p. 82–848C, yield: 70%
(84 mg). 1H NMR (CDCl3, 600 MHz): d=7.34 (d, 2H, J=8.3 Hz), 6.61
(d, 2H, J=8.3 Hz), 4.32 ppm (s, 2H); 13C NMR (CDCl3, 150 MHz): d=
150.6, 133.6, 133.4, 120.2, 114.2, 114.1, 99.2 ppm; EIMS: m/z 120.2 [M]+.
3-Methoxyaniline (6h):[20] Red oil; yield: 82% (101 mg); 1H NMR
(CDCl3, 600 MHz): d=7.05 (dd, 1H, J=8.3, 7.6 Hz), 6.32 (dd, 1H, J=
2.1, 8.3 Hz), 6.29 (dd, 1H, J=2.1, 7.6 Hz), 6.24 (t, 1H, J=2.1 Hz), 3.75 (s,
3H), 3.64 ppm (s, 2H); 13C NMR (CDCl3, 150 MHz): d=160.7, 147.7,
130.0, 107.8, 103.9, 101.0, 55.0 ppm; EIMS: m/z 123.1 [M]+.
3-Chloroaniline (6i):[20] Colorless oil; yield: 70% (89 mg); 1H NMR
(CDCl3, 600 MHz): d=7.05 (dd, 1H, J=7.6, 8.3 Hz), 6.71 (d, 1H, J=
7.6 Hz), 6.66 (s, 1H), 6.53 (d, 1H, J=8.3 Hz), 3.71 ppm (s, 2H);
13C NMR (CDCl3, 150 MHz): d=147.6, 134.8, 130.3, 118.4, 114.9,
113.1 ppm. EIMS: m/z: 127.0 [M]+.
(3-Aminophenyl)methanol (6j):[20] Colorless soild; m.p. 91–938C; yield:
76% (94 mg); 1H NMR (CDCl3, 600 MHz): d=7.14 (t, 1H, J=7.6 Hz),
6.74 (d, 1H, J=7.6 Hz), 6.70 (s, 1H), 6.61 (m, 1H), 4.60 (s, 2H),
3.69 ppm (s, 2H); 13C NMR (CDCl3, 150 MHz): d=146.6, 142.2, 129.5,
117.1, 114.4, 113.5, 65.4 ppm; ESIMS: m/z: 124.2 [M+H]+.
3-Nitroaniline (6k):[20] Yellow solid; m.p. 113–1158C; yield: 70%
(97 mg); 1H NMR (CDCl3, 600 MHz): d=7.57 (dd, 1H, J=2.1, 8.3 Hz),
7.49 (t, 1H, J=2.1 Hz), 7.26 (d, 1H, J=8.3 Hz), 6.95 (dd, 1H, J=2.1,
8.3 Hz), 4.00 ppm (s, 2H); 13C NMR (CDCl3, 150 MHz): d=149.2, 147.3,
129.9, 120.6, 113.2, 109.0 ppm; EIMS: m/z 138.1 [M]+.
o-Toluidine (6l):[12c] Red oil; yield: 70% (75 mg); 1H NMR (CDCl3,
600 MHz): d=7.04 (m, 2H), 6.71 (t, 1H, J=7.6 Hz), 6.67 (d, 1H, J=
7.6 Hz), 3.58 (s, 2H), 2.17 ppm (s, 3H); 13C NMR (CDCl3, 150 MHz): d=
144.5, 130.4, 126.9, 122.3, 118.6, 114.9, 17.3 ppm; EIMS: m/z: 107.1 [M]+.
2-Bromoaniline (6m):[20] White solid; m.p. 30–318C; yield: 78%
(134 mg); 1H NMR (CDCl3, 600 MHz): d=7.40 (dd, 1H, J=1.4, 8.3 Hz),
7.60 (m, 1H), 6.76 (dd, 1H, J=1.4, 8.3 Hz), 6.61 (m, 1H), 4.06 ppm (s,
2H); 13C NMR (CDCl3, 150 MHz): d=144.0, 132.5, 128.3, 119.4, 115.8,
109.4 ppm; EIMS: m/z: 171.0, 173.0 [M]+.
Naphthalen-1-amine (6n):[20] Red solid; m.p. 48–508C; yield: 70%
(100 mg); 1H NMR (CDCl3, 600 MHz): d=7.80 (m, 2H), 7.45 (m, 2H),
7.29 (m, 2H), 6.77 (d, 1H, J=6.9 Hz), 4.14 ppm (s, 2H); 13C NMR
(CDCl3, 150 MHz): d=142.0, 134.4, 128.5, 126.3, 125.8, 124.8, 123.6,
120.7, 118.9, 109.6 ppm; EIMS: m/z: 143.1 [M]+.
Nitrobenzene (7a):[21a] Eluent: ethyl acetate/petroleum ether (1:20);
yellow oil, yield: 60% (74 mg); 1H NMR (CDCl3, 600 MHz): d=8.16 (d,
2H, J=7.6), 7.68 (t, 1H, J=7.6 Hz), 7.52 ppm (t, 2H, J=7.6 Hz);
13C NMR (CDCl3, 150 MHz): d=147.7, 134.3, 128.9, 122.9 ppm; EIMS:
m/z: 123.0 [M]+.
4-Nitrobenzoic acid (7 f):[45] Eluent: ethyl acetate/petroleum ether (1:5);
yellow solid; m.p. 229–2318C; yield: 54% (90 mg); 1H NMR (CDCl3,
600 MHz): d=13.7 (s, 1H), 8.33 (d, 2H, J=8.2 Hz), 8.18 ppm (d, 2H, J=
8.2 Hz); 13C NMR (CDCl3, 150 MHz): d=166.3, 150.6, 136.9, 131.2,
124.3 ppm; ESIMS: m/z: 166.1 [MÀH]À.
3-Nitroanisole (7g):[46] Eluent: ethyl acetate/petroleum ether (1:20);
yellow oil; yield: 54% (83 mg); 1H NMR (CDCl3, 600 MHz): d=7.83
(dd, 1H, J=2.1, 8.3 Hz), 7.74 (dd, 1H, J=2.1, 2.8 Hz), 7.43 (t, 1H, J=
8.3 Hz), 7.23 (dd, 1H, J=2.8, 8.3 Hz), 3.90 ppm (s, 3H); 13C NMR
(CDCl3, 150 MHz): d=160.1, 149.2, 129.9, 121.3, 115.8, 108.1, 55.8 ppm;
EIMS: m/z: 153.0 [M]+.
3-Nitrochlorobenzene (7h):[21a] Eluent: ethyl acetate/petroleum ether
(1:20); yellow solid; m.p. 46–478C; yield: 60% (94 mg); 1H NMR
(CDCl3, 600 MHz): d=8.24 (s, 1H), 8.14 (d, 1H, J=8.3 Hz), 7.69 (d, 1H,
J=8.3 Hz), 7.51 ppm (t, 1H, J=8.3 Hz); 13C NMR (CDCl3, 150 MHz):
d=148.8, 135.4, 134.7, 130.3, 123.8, 121.6 ppm; EIMS: m/z: 157.0 [M]+.
3-Nitrobenzyl alcohol (7i):[47] Eluent: ethyl acetate/petroleum ether
(1:20); yellow oil; yield: 50% (77 mg); 1H NMR (CDCl3, 300 MHz): d=
8.25 (s, 1H), 8.15 (d, 1H, J=8.3 Hz), 7.70 (d, 1H, J=8.3 Hz), 7.54 (t, 1H,
J=8.3 Hz), 4.83 ppm (s, 2H); 13C NMR (CDCl3, 75 MHz): d=148.3,
142.8, 132.6, 129.4, 122.5, 121.5, 64.0 ppm; EIMS: m/z: 153.0 [M]+.
3-Nitroaniline (7j): Eluent: ethyl acetate/petroleum ether (1:10); yellow
solid; m.p. 94–968C; yield: 64% (88 mg); 1H NMR (CDCl3, 600 MHz):
d=7.57 (d, 1H, J=8.2 Hz), 7.49 (s, 1H), 7.27 (t, 1H, J=8.2 Hz), 6.95 (d,
2H, J=8.2 Hz), 4.00 ppm (s, 2H); 13C NMR (CDCl3, 150 MHz): d=
149.3, 147.4, 129.9, 120.6, 113.1, 109.0 ppm; EIMS: m/z: 138.1 [M]+.
3-Nitrobenzoic acid (7k):[47] Eluent: ethyl acetate/petroleum ether (1:5);
white solid; m.p. 142–1438C; yield: 60% (100 mg); 1H NMR (CDCl3,
600 MHz): d=13.71 (s, 1H), 8.62 (d, 1H, J=1.4 Hz), 8.47 (dd, 1H, J=
1.4, 8.3 Hz), 8.35 (d, 1H, J=7.6 Hz), 7.82 ppm (dd, 1H, J=8.3, 7.6 Hz);
13C NMR (CDCl3, 150 MHz): d=166.0, 148.4, 135.9, 133.0, 131.1, 127.9,
124.2 ppm; ESIMS: m/z: 166.3 [MÀH]À.
1-Bromo-2-nitrobenzene (7l):[44] Eluent: ethyl acetate/petroleum ether
(1:10); yellow oil; yield: 44% (89 mg); 1H NMR (CDCl3, 600 MHz): d=
7.84 (d, 1H, J=7.6 Hz), 7.75 (d, 1H, J=8.3 Hz), 7.46 ppm (m, 2H);
13C NMR (CDCl3, 150 MHz): d=149.9, 135.0, 133.2, 128.2, 125.5,
114.4 ppm; EIMS: m/z: 201.0, 203.0 [M]+.
Acknowledgements
The authors wish to thank the National Natural Science Foundation of
China (grant no. 20972083) and the Ministry of Science and Technology
of China (2009ZX09501-004) for financial support.
4-Nitrotoluene (7b):[44] Eluent: ethyl acetate/petroleum ether (1:20);
yellow solid; m.p. 52–538C; yield: 65% (89 mg); 1H NMR (CDCl3,
600 MHz): d=8.11 (d, 2H, J=8.9 Hz), 7.32 (d, 2H, J=8.3 Hz), 2.47 ppm
[1] J. Hassan, M. Sevignon, C. Gozzi, E. Schulz, M. Lemaire, Chem.
Rev. 2002, 102, 1359.
Chem. Eur. J. 2011, 17, 5652 – 5660
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5659

H. Fu et al.
[2] Metal-Catalyzed Cross-coupling Reactions (Eds.: F. Diederich, P. J.
Stang), Wiley-VCH, Weinheim, 1997.
[3] E. F. V. Scriven, K. Turnbull, Chem. Rev. 1988, 88, 297.
[4] K. Schank in The Chemistry of Sulfones and Sulfoxides (Eds.:S.
Patai, Z. Rappoport, C. J. M. Stirling), Wiley, New York, 1988,
Chapter 7.
[5] Z. Rappoport, The Chemistry of Phenols, Wiley-VCH, Weinheim,
2003.
[6] S. A. Lawrence, Amines: Synthesis Properties and Application. Cam-
bridge University Press, Cambridge, 2004.
[17] For the synthesis of aryl azides, see: a) Y. Li, L.-X. Gao, F.-S. Han,
Chem. Eur. J. 2010, 16, 7969; b) C. Tao, X. Cui, J. Li, A. Liu, L. Liu,
Q. Guo, Tetrahedron Lett. 2007, 48, 3525.
[18] For the synthesis of aryl sulfones, see: A. Kar, I. A. Sayyed, W. F.
Lo, H. M. Kaiser, M. Beller, M. K. Tse, Org. Lett. 2007, 9, 3405.
[19] For the synthesis of phenols, see: J. Xu, X. Wang, C. Shao, D. Su, G.
Cheng, Y. Hu, Org. Lett. 2010, 12, 1964.
[20] For the synthesis of arylamines, see: H. Rao, H. Fu, Y. Jiang, Y.
Zhao, Angew. Chem. 2009, 121, 1134; Angew. Chem. Int. Ed. 2009,
48, 1114.
[21] For the synthesis of nitroarenes, see: a) G. K. S. Prakash, C. Panja,
T. Mathew, V. Surampudi, N. A. Petasis, G. A. Olah, Org. Lett. 2004,
6, 2205; b) G. K. S. Prakash, T. Mathew, Angew. Chem. 2010, 122,
1771; Angew. Chem. Int. Ed. 2010, 49, 1726.
[7] W. E. Muller, The Benzodiazepine Receptor, Cambridge University
Press, Cambridge, 1988.
[8] A. Klapars, S. L. Buchwald, J. Am. Chem. Soc. 2002, 124, 14844.
[9] W. Zhu, D. Ma, Chem. Commun. 2004, 888.
[22] a) D. M. T. Chan, P. Y. S. Lam in Boronic Acids (Ed.: D. G. Hall),
Wiley, New York, 2005; pp. 205–240; b) P. Y. S. Lam, C. G. Clark, S.
Saubern, J. Adams, M. P. Winters, D. M. T. Chan, A. Combs, Tetra-
hedron Lett. 1998, 39, 2941.
[23] R. H. Seevers, R. E. Counsell, Chem. Rev. 1982, 82, 575.
[24] J. March, Advanced Organic Chemistry 4th ed. Wiley-Interscience,
New York, 2000.
[10] S. Cacchi, G. Fabrizi, A. Goggiamani, L. M. Parisi, R. Bernini, J.
Org. Chem. 2004, 69, 5608.
[11] a) K. W. Anderson, T. Ikawa, R. E. Tundel, S. L. Buchwald, J. Am.
Chem. Soc. 2006, 128, 10694; b) D. Zhao, N. Wu, S. Zhang, P. Xi, X.
Su, J. Lan, J. You, Angew. Chem. 2009, 121, 8885–8888; Angew.
Chem. Int. Ed. 2009, 48, 8729–8732; c) A. Tlili, N. Xia, F. Monnier,
M. Taillefer, Angew. Chem. 2009, 121, 8881; Angew. Chem. Int. Ed.
2009, 48, 8725.
[12] a) Q. Shen, J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 10028; b) N.
Xia, M. Taillefer, Angew. Chem. 2009, 121, 343; Angew. Chem. Int.
Ed. 2009, 48, 337; c) H. Xu, C. Wolf, Chem. Commun. 2009, 3035.
[13] B. P. Fors, S. L. Buchwald, J. Am. Chem. Soc. 2009, 131, 12898.
[14] a) T. Ishiyama, M. Murata, N. Miyaura, J. Org. Chem. 1995, 60,
7508; b) M. Murata, S. Watanabe, Y. Masuda, J. Org. Chem. 1997,
62, 6458; c) M. Murata, T. Oyama, S. Watanabe, Y. Masuda, J. Org.
Chem. 2000, 65, 164; d) C. Kleeberg, L. Dang, Z. Lin, T. B. Marder,
Angew. Chem. 2009, 121, 5454; Angew. Chem. Int. Ed. 2009, 48,
5350.
[15] a) I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy, J. F.
Hartwig, Chem. Rev. 2010, 110, 890; b) J. Y. Cho, M. K. Tse, D.
Holmes, R. J. Maleczka, M. R. Smith, Science 2002, 295, 305;
c) T. M. Boller, J. M. Murphy, M. Hapke, T. Ishiyama, N. Miyaura,
J. F. Hartwig, J. Am. Chem. Soc. 2005, 127, 14263; d) I. A. I. Mkhal-
id, D. N. Coventry, D. Albesa-Jove, A. S. Batsanov, J. A. K. Howard,
R. N. Perutz, T. B. Marder, Angew. Chem. 2006, 118, 503; Angew.
Chem. Int. Ed. 2006, 45, 489; e) S. Kawamorita, H. Ohmiya, K.
Hara, A. Fukuoka, M. Sawamura, J. Am. Chem. Soc. 2009, 131,
5058.
[16] For the synthesis of aryl halides, see: a) G. W. Kabalka, E. E.
Gooch, J. Org. Chem. 1980, 45, 3578; b) G. W. Kabalka, E. E.
Gooch, J. Org. Chem. 1981, 46, 2582; c) G. W. Kabalka, V. Namboo-
diri, M. R. Akula, J. Labelled Compd. Radiopharm. 2001, 44, 921;
d) G. W. Kabalka, A. R. Mereddy, Organometallics 2004, 23, 4519;
e) R. H. Szumigala, P. N. Devine, D. R. Gauthier, R. P. Volante, J.
Org. Chem. 2004, 69, 566; f) A. L. S. Thompson, G. W. Kabalka,
M. R. Alkula, J. W. Huffman, Synthesis 2005, 547; g) J. M. Murphy,
X. Liao, J. F. Hartwig, J. Am. Chem. Soc. 2007, 129, 15434; h) T.
Furuya, T. Ritter, J. Am. Chem. Soc. 2008, 130, 10060; i) T. Furuya,
T. Ritter, Org. Lett. 2009, 11, 2860; j) H. Wu, J. Hynes, Jr., Org. Lett.
2010, 12, 1192; k) M.-L. Yao, M. S. Reddy, L. Yong, I. Walfish, D. W.
Blevins, G. W. Kabalka, Org. Lett. 2010, 12, 700; l) G. W. Kabalka,
A. R. Mereddy, Tetrahedron Lett. 2004, 45, 343; m) L. Yong, M.-L.
Yao, J. F. Green, H. Kelly, G. W. Kabalka, Chem. Commun. 2010,
46, 2623; n) G. W. Kabalka, K. A. R. Sastry, H. C. Hsu, M. D. Hylar-
ides, J. Org. Chem. 1981, 46, 3113; o) G. W. Kabalka, M. R. Akula, J.
Zhang, Nucl. Med. Biol. 2002, 29, 841; p) G. W. Kabalka, M.-L. Yao,
J. Organomet. Chem. 2009, 694, 1638; q) G. W. Kabalka, G. Tang,
A. R. Mereddy, J. Labelled Compd. Radiopharm. 2007, 50, 446;
r) G. W. Kabalka, R. S. Varma, Y.-Z. Gai, R. M. Baldwin, Tetrahe-
dron Lett. 1986, 27, 3843; s) C. Thiebes, G. K. S. Prakash, N. A. Peta-
sis, G. A. Olah, Synlett 1998, 141.
[25] G. Stavber, J. Iskra, M. Zupan, S. Stavber, Adv. Synth. Catal. 2008,
350, 2921.
[26] O. V. Branytska, R. Neumann, J. Org. Chem. 2003, 68, 9510.
[27] S. Farhadi, Z. Momeni, J. Mol. Catal. A 2007, 277, 47.
[28] F. W. Foss, Jr., T. P. Mathews, Y. Kharel, P. C. Kennedy, A. H.
Snyder, M. D. Davis, K. R. Lynch, T. L. Macdonald, Bioorg. Med.
Chem. 2009, 17, 6123.
[29] A. R. Hajipour, M. Arbabian, A. E. Ruoho, J. Org. Chem. 2002, 67,
8622.
[30] V. L. Blair, W. Clegg, R. E. Mulvey, L. Russo, Inorg. Chem. 2009,
48, 8863.
[31] I. L. Reich, H. J. Reich, J. Org. Chem. 1981, 46, 3721.
[32] S. Tchilibon, B. V. Joshi, S. K. Kim, H. T. Duong, Z. G. Gao, K. A.
Jacobson, J. Med. Chem. 2005, 48, 1745.
[33] C. Y. Lo, M. P. Kumar, H. K. Chang, S. F. Lush, R. S. Liu, J. Org.
Chem. 2005, 70, 10482.
[34] P. Pawlucꢂ, G. Hreczycho, J. Szudkowska, M. Kubicki, B. Marciniec,
Org. Lett. 2009, 11, 3390.
[35] M. A. Fazio, O. P. Lee, D. I. Schuster, Org. Lett. 2008, 10, 4979.
[36] J. T. Spletstoser, P. T. Flaherty, R. H. Himes, G. I. Georg, J. Med.
Chem. 2004, 47, 6459.
[37] M. Pudlo, D. Csanyi, F. Moreau, G. Hajos, Z. Riedl, J. Sapi, Tetrahe-
dron 2007, 63, 10320.
[38] S. P. Klump, H. Shechter, Tetrahedron Lett. 2002, 43, 8421.
[39] M. Peyronneau, M. T. Boisdon, N. Roques, S. Mazieres, C. L. Roux,
Eur. J. Org. Chem. 2004, 4636.
[40] P. Hanson, R. A. A. J. Hendrickx, J. R. L. Smith, Org. Biomol.
Chem. 2008, 6, 745.
[41] B. P. Bandgar, S. V. Bettigeri, J. Phopase, Org. Lett. 2004, 6, 2105.
[42] D. Yang, H. Fu, Chem. Eur. J. 2010, 16, 2366.
[43] A. G. Sergeev, T. Schulz, C. Torborg, A. Spannenberg, H. Neumann,
M. Beller, Angew. Chem. 2009, 121, 7731; Angew. Chem. Int. Ed.
2009, 48, 7595.
[44] K. B. Saitanya, H. Sahid, K. Manoranjan, K. C. Mihir, Catal.
Commun. 2008, 9, 919.
[45] A. Chacko, B. Mathew, J. Appl. Polym. Sci. 2003, 90, 3708.
[46] J. Cornella, C. Sanchez, D. Banawa, I. Larrosa, Chem. Commun.
2009, 7176.
[47] A. Chacko, R. Devi, S. Abraham, B. Mathew, J. Appl. Polym. Sci.
2005, 96, 1897.
Received: December 23, 2010
Published online: April 8, 2011
Please note: Minor changes have been made since the publication in
Chemistry–A European Journal Early View. The Editor.
5660
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5652 – 5660