CuI/8-hydroxyquinalidine promoted N-arylation of indole and azoles

Article abstract of DOI:10.1002/cjoc.201100433

An efficient catalytic system of CuI/8-hydroxyquinalidine was developed for the coupling of aryl iodides and indole as well as some azoles. The reaction could be carried out at 90°C under the condition of relatively low catalyst loading, affording various

Full text of DOI:10.1002/cjoc.201100433

FULL PAPER
DOI: 10.1002/cjoc.201100433
CuI/8-Hydroxyquinalidine Promoted N-Arylation of Indole and
Azoles†
Yang, Xinyea(杨新业)
Xing, Huia(邢辉)
Zhang, Yea(张烨)
Lai, Yishenga(赖宜生)
Ma, Daweib(马大为)
Zhang, Yihua*,a(张奕华)
Jiang, Yongwen*,b(蒋咏文)
a Center of Drug Discovery, China Pharmaceutical University, Nanjing 210009, China
b State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China
An efficient catalytic system of CuI/8-hydroxyquinalidine was developed for the coupling of aryl iodides and
indole as well as some azoles. The reaction could be carried out at 90 ℃ under the condition of relatively low cata-
lyst loading, affording various N-arylindoles and N-aryl azoles in good yields. The functionalized and hindered aryl
iodides were suitable substrates for this transformation.
Keywords copper, Ullmann reaction, 8-hydroxyquinalidine, cross-coupling, indole, azoles
Introduction
pling reaction of aryl iodides with indole and azoles
efficiently at 90 ℃ under relatively low loading (2
mol% of CuI and 4 mol% of 8-hydroxyquinalidine).
Herein, we wish to detail the results.
N-Arylindoles as well as N-aryl azoles are very im-
portant core skeletons in numerous natural products and
pharmaceutical compounds.[1] They could be used as
antipsychotic agents,[2] cyclooxygenase (COX)-1 in-
hibitors,[3] COX-2 inhibitors,[4] 5-HT6 receptor antago-
nists,[5] anti-HIV-1 agents[6] and herbicides.[7]
Results and Discussion
Initially, we used the coupling of 4-iodoanisole and
indole as the model and screened a series of ligands un-
der the conditions of 2 mol% CuI, 4 mol% ligand,
K2CO3 as the base and DMSO as the solvent at 90 ℃
for 24 h. It was found that some reported efficient
ligands such as L-proline (L1),[10] 8-hydroquinoline
(L2),[16] 1,10-phen (L4),[11] N,N-dimethylethylenedia-
mine (L5)[12] and pyrrole 2-carboxylic acid (L7)[19] only
afforded low yields under the condition of low catalyst
loading (Table 1, Entries 1, 2, 4, 5, 7). 8-Hydroxyqui-
nalidine (L3) afforded the best result (Entry 3) while
2-picolinic acid (L6)[20] also got the N-aryl indole in
90% yield (Entry 6). It seemed that the ligand is crucial
for this transformation, as an evidence that only 20%
yield was obtained in the absence of the ligand (Entry 8).
The combination of K2CO3 and DMSO was found as a
more suitable system by screening the bases and the
solvents (Entry 3 vs. Entries 9—16). When the catalyst
loading was further reduced to 1 mol%, the yield also
decreased slightly (Entry 17). In addition, decreasing
the reaction temperature to 70 ℃ got poor result (Entry
18). However, the reaction was carried out well at 40
℃ when 10 mol% of CuI and 20 mol% of 8-hydroxy-
quinalidine were used (Entry 19). It indicated that the
Ullmann coupling reaction is a classical method for
the formation of C—N bond although the high reaction
temperature is required.[8] In past decade, great progress
in ligand-promoted Ullmann-type coupling reactions
makes the coupling of aryl halides with conjugated ni-
trogen-containing heterocycles carry out under mild
reaction conditions.[9] For example, amino acids,[10]
1,10-phenanthroline,[11] diamines,[12] BINOL,[13] Sa-
lox,[14] N-hydroxyimides,[15] 8-hydroxyquinoline[16] and
so on are very efficient for this transformation. However,
in most cases a relatively high loading of the catalytic
system, at least 5 mol% of copper salt and 10 mol% of
ligand for N-arylation of indole, was essential for get-
ting the satisfied yields. In addition, the coupling of in-
dole with hindered 2-substituted aryl iodides required
higher reaction temperature (120 ℃).[17] Recently, Teo
and coworkers developed a ligand-free Cu2O-catalyzed
strategy for the N-arylation of indole and azoles under
the promotion of phase transfer catalyst in water.[18]
While 10 mol% of Cu2O and high reaction temperature
(130 ℃) were necessary. As an extension of our re-
search work,[9d] we found that CuI/8-hydroxyquinalidine
as a powerful catalytic system could promote the cou-
*
E-mail: jiangyw@mail.sioc.ac.cn & zyhtgd@sohu.com
Received September 30, 2011; accepted November 29, 2011; published online March 7, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201100433 or from the author.
† Dedicated to Professor Weiyuan Huang on the occasion of his 90th birthday.
Chin. J. Chem. 2012, 30, 875—880
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Yang et al.
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reaction temperature was very important for this cou-
pling under the condition of low catalyst loading. For
less active 4-bromoanisole, even increasing the amount
of catalyst and reaction temperature only got low yield
(Entry 20).
Then various aryl iodides and indoles were investi-
gated for this transformation. As summarized in Table 2,
both electron-withdrawing and electron-donating aryl
iodides could be converted into the corresponding
N-arylindoles 3b—3j in excellent yields (Entries 1, 2—
10). For 3-nitro-iodobenzene and 4-iodo-phenylamine,
shortening the reaction time could get good results pos-
sibly because the products were unstable at high tem-
perature (Entries 7 and 8). It is notable that the coupling
of steric hindered 2-substituted aryl iodides with indole
worked well, affording the N-arylindoles 3k—3o in
moderate to good yields (Entries 11—17). Increasing
the amount of catalysts got better results (Entries 11, 13
vs. 12, 14). For 2-methyl indole, slightly low yield was
obtained (Entry 18). In addition, 1H-pyrrolo[2,3-b]pyri-
dine as well as 2-iodothiophene, 2-iodopyridine and
3-iodopyridine were available substrates for this trans-
formation and the N-arylation products 3q—3t were
isolated in excellent yields (Entries 19—22). Regret-
fully, under our reaction conditions, aryl bromides were
less active for this coupling, only affording N-aryl in-
doles in low yields (Entries 2 and 23).
The catalytic system was also suitable for N-aryl-
ation of some other azoles such as imidazole, pyrazole,
triazole, pyrrole, benzimidazole and carbazole (Table 3).
When pyrrole and carbazole were used as the nucleo-
philes, 5 mol% of CuI and 10 mol% of 8-hydroxyqui-
nalidine were required (Entries 4 and 6).
Table 1 Screening the reaction condtions for the coupling of 4-iodoanisole and indolea
H
I
N
N
2 mol% CuI, 4 mol% L
Base, solvent
+
MeO
MeO
2a
3a
1a
H
N
NH HN
COOH
COOH
N
N
N
H
N
N
COOH
N
OH
L3
OH
L4
L5
L1
L2
L6
L7
Entry
Ligand (mol%)
Copper source (mol%)
Base
Solvent
Temp./℃
Yieldb/%
1
2
L1 (2)
L2 (2)
L3 (2)
L4 (2)
L5 (2)
L6 (2)
L7 (2)
—
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuI (4)
CuBr (4)
CuCl (4)
CuI (2)
CuI (4)
CuI (20)
CuI (10)
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
K3PO4
Na2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
70
40
110
50
23
97
42
37
90
47
20
84
52
—
50
82
—
50
80
82
64
85
40
3
4
5
6
7
8
9
L3 (2)
L3 (2)
L3 (2)
L3 (2)
L3 (2)
L3 (2)
L3 (2)
L3 (2)
L3 (1)
L3 (2)
L3 (10)
L3 (5)
10
11
12
13
14
15
16
17
18
19
20c
NMP
Dioxane
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
a Reaction conditions: 4-iodoanisole (1 mmol), indole (1.2 mmol), CuI (0.02 mmol), ligand (0.04 mmol), and K2CO3 (2.5 mmol) in
DMSO (2 mL) under Ar atmosphere, 90 ℃, 24 h. b Isolated yield. c 4-Bromoanisole was used, 36 h.
876
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CuI/8-Hydroxyquinalidine Promoted N-Arylation of Indole and Azoles
Table 2 CuI/8-Hydroxyquinalidine-catalyzed coupling of aryl halides and indolea
H
R
X
N
N
CuI (2 mol%), L3 (4 mol%)
R
+
K2CO3, DMSO, 90 oC
3
2
1
X = I, Br
Entry
Product
Yieldb/%
Entry
Product
Yieldb/%
N
N
1
2
92
30c,d
13
14
76
87f
3b
3l
CF3
N
N
O
3
4
5
98
93
94
15
16
17
52d
3c
3m
HOOC
N
N
89
F
F
3d
3n
N
Cl
N
78
3e
3o
NC
N
N
6
94
18
45d
MeO
MeO
3f
3p
N
N
7
8
92e
78e
85
19
20
21
22
97
93
98
98
N
O2N
3g
3q
N
H2N
N
S
3h
3i
3r
Ph
N
N
N
9
3s
N
N
N
10
91
3j
3t
Chin. J. Chem. 2012, 30, 875—880
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Continued
Yield b/%
Entry
Product
Yieldb/%
Entry
Product
OCH3
N
N
11
12
75
82f
23
31c,d
3k
3u
a Reaction conditions: aryl iodide (1 mmol), Indole (1.2 mmol), CuI (0.02 mmol), L3 (0.04 mmol), and K2CO3 (2.5 mmol) in DMSO (2
mL) under Ar atmosphere, 90 ℃, 24 h. b Isolated yield. c Ary bromide was used, 110 ℃, 36 h. d 0.05 mmol of CuI and 0.1 mmol of L3
were used. e 16 h. f 0.1 mmol of CuI and 0.2 mmol of L3 were used and the reaction was stirred at 40 ℃ for 48 h.
Table
3
CuI/8-hydroxyquinalidine-catalyzed coupling of
Conclusions
4-iodoanisole and azolesa
As a conclusion, we developed an efficient catalytic
system of CuI/8-hydroxyquinalidine for the coupling of
aryl iodides and indole as well as some azoles. The re-
action could be carried out at 90 ℃ under the condition
of relatively low catalyst loading, affording various
N-arylindoles and N-aryl azoles in good yields. The
functionalized and hindered aryl iodides were suitable
substrates for this transformation. This method would be
applicable in the synthesis of some pharmaceutical
compounds.
Z
CuI (2 mol%),
L3 (4 mol%)
I
N
Z
Y
HN
+
Y
K2CO3, DMSO,
90 oC
MeO
MeO
5
1
4
Y = N, C
Z = N, C
Y = N, C
Z = N, C
Entry
1
Het-NH
Product
5a
Yieldb/%
98
Experimental
H
N
MeO
MeO
N
N
General procedure for CuI/8-hydroxyquinalidine-
catalyzed coupling reaction of aryl iodides with in-
dole and azoles
N
N
4a
H
A Schlenk tube was charged with aryl iodide (1.0
mmol), indole or azole (1.2 mmol), CuI (0.02 mmol),
8-hydroxyquinalidine (0.04 mmol), K2CO3 (2.5 mmol),
and 2 mL of DMSO, evacuated and backfilled with ar-
gon. The reaction mixture was stirred at 90 ℃ for 24 h.
The cooled reaction mixture was partitioned between
ethyl acetate and water. The organic layer was washed
with water, brine, and dried over Na2SO4, and concen-
trated in vacuo. The residue was purified by column
chromatography on silica gel to provide the desired
product.
N
N
N
2
3
4
5
95
90
4b
5b
H
N
N
N
MeO
MeO
N
N
N
N
5c
4c
H
N
85c
95
1-(4-Methoxyphenyl)-1H-indole (3a)[21] 1H NMR
(300 MHz, CDCl3) δ: 7.68 (d, J＝8.1 Hz, 1H), 7.45 (d,
J＝8.1 Hz, 1H), 7.41 (d, J＝9.0 Hz, 2H), 7.27 (d, J＝
3.3 Hz, 1H), 7.22—7.12 (m, 2H), 7.03 (m, J＝9.3 Hz,
2H), 6.65 (d, J＝3.0 Hz, 1H), 3.88 (s, 3H); ESI-MS m/z:
224.0 (M＋H)＋.
4d
5d
N
H
N
N
N
MeO
4e
5e
1-Phenyl-1-indole (3b)[18] 1H NMR (300 MHz,
CDCl3) δ: 7.68 (d, J＝7.5 Hz, 1H), 7.57 (d, J＝8.0 Hz,
1H), 7.50—7.51 (m, 4H), 7.32—7.37 (m, 2H), 7.15—
7.24 (m, 2H), 6.68 (d, J＝3.1 Hz, 1H); ESI-MS m/z:
194.1 (M＋H)＋.
H
N
N
6
91c
1-[4-(1H-Indol-1-yl)phenyl]ethanone (3c)[21] 1H
NMR (300 MHz, CDCl3) δ: 8.13 (d, J＝8.4 Hz, 2H),
7.68—7.60 (m, 4H), 7.38 (d, J＝3.3 Hz, 1H), 7.30—
7.18 (m, 2H), 6.74 (d, J＝3.6 Hz, 1H), 2.66 (s, 3H);
ESI-MS m/z: 236.2 (M＋H)＋.
MeO
4f
5f
a Reaction conditions: 4-iodoanisole (1 mmol), azole (1.2 mmol),
CuI (0.02 mmol), L3 (0.04 mmol), and K2CO3 (2.5 mmol) in
DMSO (2 mL) under Ar atmosphere, 90 ℃, 24 h. b Isolated yield.
c 0.05 mmol of CuI and 0.1 mmol of L3 were used.
4-(1H-Indol-1-yl)benzoic acid (3d) 1H NMR (300
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CuI/8-Hydroxyquinalidine Promoted N-Arylation of Indole and Azoles
MHz, DMSO-d6) δ: 13.08 (brs, 1H), 8.13 (d, J＝7.8 Hz,
2H), 7.76—7.67 (m, 5H), 7.28—7.14 (m, 2H), 6.76 (d,
J＝3.0 Hz, 1H); 13C NMR (100 MHz, DMSO-d6) δ:
167.0, 143.0, 134.9, 131.3 (2C), 129.7, 128.3, 128.2,
123.2 (2C), 123.0, 121.4, 121.0, 110.8, 104.9; ESI-MS
m/z: 235.9 (M－H)－; HRMS (ESI) calcd for C15H10NO2
(M－H)－ 236.07115, found 236.07170
1-(2-(Trifluoromethyl)phenyl)-1H-indole (3m)[26]
1H NMR (300 MHz, CDCl3) δ: 7.90 (d, J＝7.5 Hz, 1H),
7.71—7.64 (m, 2 H), 7.61 (t, J＝7.5 Hz, 1H), 7.47 (d,
J＝7.8 Hz, 1H), 7.23—7.17 (m, 3H), 7.06—7.00 (m,
1H), 6.71 (d, J＝3.3 Hz, 1H); ESI-MS m/z: 262.2 (M＋
H)＋.
1-(2,4-Difluorophenyl)-1H-indole (3n) 1H NMR
(300 MHz, CDCl3) δ: 7.69 (d, J＝7.2 Hz, 1H), 7.51—
7.44 (m, 1H), 7.25—7.15 (m, 4H), 7.10—7.00 (m, 2H),
6.71 (d, J＝2.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ:
161.5 (dd, J＝10.9, 248.1 Hz), 157.2 (dd, J＝12.4,
252.1 Hz), 136.7, 128.9 (dd, J＝2.0, 10.4 Hz), 128.8,
128.6 (d, J＝1.4 Hz), 123.8 (dd, J＝4.1, 12.9 Hz), 122.6,
121.2, 120.7, 111.9 (dd, J＝3.8, 22.3 Hz), 110.3 (d, J＝
1.1 Hz), 105.4 (dd, J＝23.4, 49.4 Hz), 104.0; ESI-MS
m/z: 230.1 (M＋H)＋; HRMS (ESI) calcd for C14H10F2N
(M＋H)＋ 230.07813, found 230.07758.
1-(4-Chlorophenyl)-1H-indole (3e)[18] 1H NMR
(300 MHz, CDCl3) δ: 7.69 (dd, J＝1.2 Hz, 6.9 Hz, 1H),
7.52—7.41 (m, 5H), 7.29 (d, J＝3.3 Hz, 1H), 7.26—
7.15 (m, 2H), 6.69 (d, J＝2.7 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ: 138.5, 135.9, 132.1, 129.9 (2C), 129.5,
127.8, 125.6 (2C), 122.7, 121.4, 120.7, 110.4, 104.2;
ESI-MS m/z: 228.1 (M＋H)＋.
1-(4-Cyanophenyl)-1H-benzimidazole (3f)[22] 1H
NMR (300 MHz, CDCl3) δ: 7.82 (d, J＝8.4 Hz, 2H),
7.71—7.60 (m, 4H), 7.35 (d, J＝3.3 Hz, 1H), 7.30—
7.19 (m, 2H), 6.76 (d, J＝3.3 Hz, 1H); ESI-MS m/z:
219.1 (M＋H)＋.
1-Naphthylindole (3o)[27] 1H NMR (300 MHz,
CDCl3) δ: 7.96 (d, J＝7.8 Hz, 2H), 7.74 (d, J＝7.8 Hz,
1H), 7.60—7.40 (m, 5H), 7.34 (d, J＝3.0 Hz, 1H), 7.20
—7.02 (m, 3H), 6.76 (d, J＝3.0 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ: 138.1, 136.2, 134.6, 130.7, 129.9,
128.6 (2C), 128.4, 127.1, 126.8, 125.6, 125.2, 123.5,
122.3, 121.0, 120.2, 111.0, 103.0; ESI-MS m/z: 244.1
(M＋H)＋.
1-(3-Nitrophenyl)-1H-indole (3g)[23]
1H NMR
(300 MHz, CDCl3) δ: 8.40 (s, 1H), 8.20 (d, J＝8.1 Hz,
1H), 7.89—7.86 (m, 1H), 7.74—7.71 (m, 2H), 7.59 (d,
J＝8.1 Hz, 1H), 7.38 (d, J＝3.3 Hz, 1H), 7.32—7.20 (m,
2H), 6.76 (d, J＝3.3 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ: 149.0, 140.8, 135.4, 130.5, 129.7, 129.4,
127.3, 123.2, 121.5, 121.2, 120.7, 118.5, 110.0, 105.3.
ESI-MS m/z: 239.1 (M＋H)＋.
1-(4-Methoxylphenyl)-2-methyl-1H-indole (3p)[12d]
1H NMR (300 MHz, CDCl3) δ: 7.57—7.54 (m, 1H),
7.26—7.23 (m, 2H), 7.10—7.01 (m, 5H), 6.37 (s, 1H),
3.86 (s, 3H), 2.26 (s, 3H); ESI-MS m/z: 238.1 (M＋H)＋.
1-(4-Methoxyphenyl)-1H-pyrrolo[2,3-b]pyridine
(3q)[18] 1H NMR (300 MHz, CDCl3) δ: 8.38—8.36 (m,
1H), 7.99—7.96 (m, 1H), 7.59—7.63 (m, 2H), 7.46 (d,
J＝3.6 Hz, 1H), 7.12 (dd, J＝4.5, 7.5 Hz, 1H), 7.07—
7.03 (m, 2H), 6.61 (d, J＝3.3 Hz, 1H), 3.87 (s, 3H);
ESI-MS m/z: 225.1 (M＋H)＋.
4-(1H-Indol-1-yl)benzenamine (3h)
1H NMR
(300 MHz, CD3OD) δ: 7.59 (d, J＝7.8 Hz, 1H), 7.36 (d,
J＝7.8 Hz, 1H), 7.27 (d, J＝3.0 Hz, 1H),7.2 (d, J＝8.7
Hz, 2H), 7.13—7.02 (m, 2H), 6.85 (d, J＝8.7 Hz, 2H),
6.56 (d, J＝3.0 Hz, 1H); 13C NMR (100 MHz, CD3OD)
δ: 147.9, 137.9, 131.7, 130.4, 129.5, 126.9 (2C), 122.9,
121.8, 120.8, 117.0 (2C), 111.4, 103.3; ESI-MS m/z:
209.0 (M＋H)＋; HRMS (ESI) calcd for C14H13N2 (M＋
H)＋ 209.10787, found 209.10732.
1-Thiophen-2-yl-1H-indole (3r)[11f] 1H NMR (300
MHz, CDCl3) δ: 7.66 (d, J＝6.3 Hz, 1H), 7.59 (d, J＝
8.1 Hz, 1H), 7.29—7.16 (m, 4H), 7.09—7.03 (m, 2H),
6.66 (d, J＝3.3 Hz, 1H); ESI-MS m/z: 200.0 (M＋H)＋.
1-Pyridin-2-yl-1H-indole (3s)[28] 1H NMR (300
MHz, CDCl3) δ: 8.58 (d, J＝3.6 Hz, 1H), 8.21 (d, J＝
8.4 Hz, 1H), 7.86—7.80 (m, 1H), 7.73 (d, J＝3.6 Hz,
1H), 7.68 (d, J＝8.1 Hz, 1H), 7.51 (d, J＝8.4 Hz, 1 H),
7.33—7.16 (m, 3H), 6.71 (d, J＝3.3 Hz, 1H); ESI-MS
m/z: 195.1 (M＋H)＋.
N-(4-Biphenyl)indole (3i)[24] 1H NMR (300 MHz,
CDCl3) δ: 7.74—7.56 (m, 8H), 7.50—7.45 (m, 2H),
7.40—7.35 (m, 2H), 7.27—7.16 (m, 2H), 6.71 (d, J＝
3.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ: 140.3,
139.4, 139.1, 135.9, 129.5, 129.0 (2C), 128.4 (2C),
128.0, 127.6, 127.2 (2C), 124.6 (2C), 122.6, 121.3,
120.6, 110.7, 103.9; ESI-MS m/z: 270.2 (M＋H)＋.
1-m-Tolyl-1H-indole (3j)[18] 1H NMR (300 MHz,
CDCl3) δ: 7.69 (d, J＝7.5 Hz, 1H), 7.58 (d, J＝8.1 Hz,
1H), 7.42—7.30 (m, 4H), 7.25—7.14 (m, 3H), 6.68 (d,
J＝3.3 Hz, 1H); ESI-MS m/z: 208.1 (M＋H)＋.
1-(Pyridin-3-yl)-1H-indole (3t)[29] 1H NMR (400
MHz, CDCl3) δ: 8.84 (d, J＝2.4 Hz, 1H), 8.61 (dd, J＝
1.6, 4.8 Hz, 1H), 7.84 (ddd, J＝1.6, 2.4, 8.0 Hz, 1H),
7.69—7.72 (m, 1H), 7.52—7.54 (m, 1H), 7.45—7.49
(m, 1H), 7.33 (d, J＝3.2 Hz, 1H), 7.18—7.28 (m, 2H),
6.74 (dd, J＝0.8, 3.2 Hz, 1H); EI-MS m/z: 194 (M＋).
1-p-Tolyl-1H-indole (3u)[30] 1H NMR (400 MHz,
CDCl3) δ: 7.67—7.68 (m, 1H), 7.51—7.53 (m, 1H),
7.37—7.39 (m, 2H), 7.29—7.31 (m, 3H), 7.13—7.24
(m, 2 H), 6.66 (dd, J＝0.8, 3.2 Hz, 1H), 2.43 (s, 3H);
ESI-MS m/z: 208.1 (M＋H)＋.
1-(2-Methoxyphenyl)-1H-indole (3k)[18] 1H NMR
(300 MHz, CDCl3) δ: 7.68 (d, J＝8.4 Hz, 1H), 7.39—
7.37 (m, 2H), 7.27 (d, J＝3.0 Hz, 1H), 7.20—7.06 (m,
5H), 6.66 (d, J＝3.3 Hz, 1H), 3.74 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ: 154.5, 136.9, 129.4, 128.6, 128.5,
128.2, 128.1, 121.9, 120.9, 120.8, 120.0, 112.5, 110.9,
102.6, 55.7; ESI-MS m/z: 224.1 (M＋H)＋.
1-o-Tolyl-1H-indole (3l)[25] 1H NMR (300 MHz,
CDCl3) δ: 7.67—7.70 (m, 1H), 7.35—7.28 (m, 4H),
7.16—7.13 (m, 3H), 7.04—7.01 (m, 1H), 6.66 (d, J＝
3.3 Hz, 1H), 2.05 (s, 3H); ESI-MS m/z: 208.1 (M＋H)＋.
1-(4-Methoxyphenyl)-1H-imidazole (5a)[21]
1H
NMR (300 MHz, CDCl3) δ: 7.76 (s, 1H), 7.29 (d, J＝
Chin. J. Chem. 2012, 30, 875—880
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
879

Yang et al.
FULL PAPER
Int. Ed. 2008, 47, 3096; (c) Evano, G.; Blanchard, N.; Toumi, M.
Chem. Rev. 2008, 108, 3054; (d) Ma, D.; Cai, Q. Acc. Chem. Res.
2008, 41, 1450; (e) Wang, Y.; Zeng, J.; Cui, X. Chin. J. Org. Chem.
2010, 30, 181.
8.7 Hz, 2H), 7.19 (d, J＝6.6 Hz, 2H), 6.98 (d, J＝9.0 Hz,
2H), 3.85 (s, 3H); ESI-MS m/z: 175.0 (M＋H)＋.
1-(4-Methoxyphenyl)-1H-pyrazole (5b)[21]
1H
NMR (300 MHz, CDCl3) δ: 7.83 (d, J＝2.1 Hz, 1H),
7.70 (d, J＝1.8 Hz, 1H), 7.57—7.60 (m, 2H), 6.92—
6.96 (m, 2H), 6.43—6.44 (m, 1H), 3.84 (s, 3H); ESI-MS
m/z: 175.0 (M＋H)＋.
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D.; Cai, Q. Synlett 2004, 128; (c) Lv, X.; Wang, Z.; Bao, W.
Tetrahedron 2006, 62, 4756; (d) Yang, C.-T.; Fu, Y.; Huang, Y.-B.;
Yi, J.; Guo, Q.-X.; Liu, L. Angew. Chem., Int. Ed. 2009, 48, 7398; (e)
Guo, X.; Rao, H.; Fu, H.; Jiang, Y.; Zhao, Y. Adv. Synth. Catal.
2006, 348, 2197.
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1999, 40, 2657; (b) Altman, R. A.; Buchwald, S. L. Org. Lett. 2006,
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Chem. 2007, 72, 6190; (d) Hosseinzadeh, R.; Tajbakhsh, M.;
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jbakhsh, M.; Alikarami, M. Tetrahedron Lett. 2006, 47, 5203; (f)
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1707.
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Chem. Soc. 2001, 123, 7727; (b) Antilla, J. C.; Klapars, A.;
Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 11684; (c) Antilla, J.
C.; Baskin, J. M.; Barder, T. E.; Buchwald, S. L. J. Org. Chem. 2004,
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Org. Chem. 2010, 6678.
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Hamada, S.; Spindler, J.-F.; Taillefer, M. Chem. Eur. J. 2004. 10,
5607.
1-(4-Methoxyphenyl)-1H-1,2,4-triazole
(5c)[31]
1H NMR (300 MHz, CDCl3) δ: 8.45 (s, 1H), 8.08 (s,
1H), 7.57 (dd, J＝2.1, 6.9 Hz, 2H), 7.02 (dd, J＝2.1, 6.9
Hz, 2H), 3.86 (s, 3H); ESI-MS m/z: 176.0 (M＋H)＋.
1-(4-Methoxyphenyl)-1H-pyrrole (5d)[32]
1H
NMR (300 MHz, CDCl3) δ: 7.32 (d, J＝8.4 Hz, 2H),
7.02 (d, J＝2.1 Hz, 2H), 6.95 (d, J＝9.0 Hz, 2H), 6.33
(d, J＝1.8 Hz, 2H), 3.85 (s, 3H); ESI-MS m/z: 174.0 (M
＋H)＋.
1-(4-Methoxyphenyl)-1H-benzoimidazole (5e)[21]
1H NMR (300 MHz, CDCl3) δ: 8.06 (s, 1H), 7.89—7.86
(m, 1H) 7.48—7.40 (m, 3H), 7.34—7.31 (m, 2H), 7.10
—7.06 (m, 2H), 3.90 (s, 3H); ESI-MS m/z: 225.1 (M＋
H)＋.
N-[(p-Methoxy)phenyl]carbazole (5f)[33]
1H
NMR (300 MHz, CDCl3) δ: 8.15—8.13 (m, 2H), 7.46—
7.24 (m, 8H), 7.12—7.09 (m, 2H), 3.91 (s, 3H); ESI-MS
m/z: 274.2 (M＋H)＋.
[15] Ma, H.-C.; Jiang, X.-Z. J. Org. Chem. 2007, 72, 8943.
[16] Liu, L.; Frohn, M.; Xi, N.; Dominguez, C.; Hungate, R.; Reider, P. J.
J. Org. Chem. 2005, 70, 10135.
Acknowledgement
[17] Verma, A. K.; Singh, J.; Larock, R. C. Tetrahedron 2009, 65, 8434.
[18] Yong, F.-F.; Teo, Y.-C.; Tay, S.-H.; Tab, B. Y.-H.; Lim, K.-H. Tet-
rahedron Lett. 2011, 52, 1161.
[19] Altman, R. A.; Anderson, K. W.; Buchwald, S. L. J. Org. Chem.
2008, 73, 5167.
The authors are grateful to National Natural Science
Foundation of China (grant 20921091 and 20872156)
for their financial support.
[20] Lam, M. S.; Lee, H. W.; Chan, A. S. C.; Kwong, F. Y. Tetrahedron
Lett. 2008, 49, 6192.
[21] Xu, Z.-L.; Li, H.-X.; Ren, Z.-G.; Du, W.-Y.; Xu, W.-C.; Lang, J.-P.
Tetrahedron 2011, 67, 5282.
[22] Colacino, E.; Martinez, J.; Lamaty, F. Tetrahedron 2010, 66, 3730.
[23] Rao, R. K.; Naidu, A. B.; Haseer, E. A.; Sekar, G. Tetrahedron 2009,
65, 4619.
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880
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 875—880