N-Heterocyclic Carbene Copper(I) Complex Catalyzed Coupling of (Hetero)aryl Chlorides and Nitrogen Heterocycles: Highly Efficient Catalytic System

Article abstract of DOI:10.1002/cjoc.201900461

A highly efficient catalytic system for the N-arylation reactions of (hetero)aryl chlorides and nitrogen heterocycles with a copper(I) complex containing a 1,10-phenanthroline analogue N-heterocyclic carbene (NHC) has been reported. The complex was characterized by ¹H NMR and ¹³C NMR spectroscopy and elemental analysis, and its structure was determined by single-crystal X-ray diffraction. The NHC-copper(I) complex was employed as pre-catalyst for Ullmann type N-arylation reactions of (hetero)aryl chlorides with various azoles. A variety of hindered and functionalized azoles and (hetero)aryl chlorides were transformed in good to excellent yields.

Full text of DOI:10.1002/cjoc.201900461

Chinese Journal
of Chemistry
CJC
中 国 化 学 - An International Journal
Accepted Article
Title: N-Heterocyclic Carbene Copper(I) Complex Catalyzed Coupling of (Hetero)aryl
Chlorides and Nitrogen Heterocycles: Highly Efficient Catalytic System
Authors: Mengyao Zhang, Yingying Zhang, Huixin Zhang, Yongfei Zeng*, Guiyan
Liu*
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Chinese Journal
of Chemistry
copper(I) complex, N-arylation reactions, N-heterocyclic carbene,
(hetero)aryl chlorides, nitrogen heterocycles
Report
CJC
中
国 化 学 - An International Journal
N-Heterocyclic Carbene Copper(I) Complex Catalyzed Coupling of
(Hetero)aryl Chlorides and Nitrogen Heterocycles: Highly Efficient
Catalytic System
Mengyao Zhang, Yingying Zhang, Huixin Zhang, Yongfei Zeng*, Guiyan Liu*
Tianjin Key Laboratory of Structure and Performance for Functional Molecules; Key Laboratory of Inorganic-Organic hybrid Functional Material Chemistry
(Tianjin Normal University); Ministry of Education; College of Chemistry, Tianjin Normal University, Tianjin, 300387, P. R. China.
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
A highly efficient catalytic system for the N-arylation reactions of (hetero)aryl chlorides and nitrogen heterocycles with a copper(I) complex containing a
1,10-phenanthroline analogue N-heterocyclic carbene (NHC) has been reported. The complex was characterized by 1H and 13C NMR spectroscopy and
elemental analysis, and its structure was determined by single-crystal X-ray diffraction. The NHC-copper(I) complex was employed as pre-catalyst for
Ullmann type N-arylation reactions of (hetero)aryl chlorides with various azoles. A variety of hindered and functionalized azoles and (hetero)aryl chlorides
were transformed in good to excellent yields.
complex was separated in 1993. [15] The use of NHCs as ligands in
Background and Originality Content
Cu/ligand catalytic systems has led to a variety of satisfactory
N-aryl heterocycles, as important organic compounds in
[16]
developments.
However, no more attention has been paid to
natural products, are widely used in medicine, biology, materials
and other fields. [1] Transition-metal-catalyzed Ullmann-type C-N
bond coupling has become a powerful and efficient tool to
synthesize them which has been widely used in organic synthesis.
the Ullmann-type N-arylation reactions of (hetero)aryl chlorides
and nitrogen heterocycles catalyzed by NHC-Cu complexes.
Herein,
a
new copper(I) complex containing
a
1,10-phenanthroline analogue NHC is reported. As a pre-catalyst,
it is applied to the N-arylation reactions of (hetero)aryl chlorides
with nitrogen heterocycles and works well with a wide range of
azoles at a low catalyst loading (1 mol %).
[2]
Copper is one of the most often used metals for this
[3]
transformation.
Unfortunately, the application of
copper-mediated N-arylation reactions in the synthesis of
N-arylated heterocyclic compounds has some challenges. These
reactions usually require elevated reaction temperatures, high
catalyst loadings, or selective halide substrates (aryl iodides or aryl
bromides). All of these limit their application in industry from a
practical point of view. In order to solve these problems and
improve catalytic efficiency, much effort has been made in the
design of ligands to promote copper-catalyzed Ullmann-type
reactions. During the past years, a series of effective ligands,
Results and Discussion
The synthetic route for copper(I) complex 2 is illustrated in
Scheme
1.
1,8-Naphthyrido[1,2-a]-(2’,6’-diisopropylphenyl)
limidazolium chloride 1 was synthesized according to previous
reports. [17] By adding commercially available CuCl and K2CO3 with
1 in the presence of acetone, the copper(I) complex 2 was
prepared. The complex was characterized by NMR spectroscopy
(see Supporting Information).
[4]
[5]
[6]
including diamines,
phenanthroline,
amino acids,
[7]
[8]
[9]
β-diketones,
8-hydroxyquinolines,
2,2’-bipyridine,
Schiff base,
carbohydrates,
ethylene
[10]
[5e, 11]
[12]
[13]
glycoll,
and others,
have been reported.
Scheme 1. Synthesis of copper(I) complex 2.
Although the above progress has been achieved, most of
the reaction halide substrates are still aryl iodides or aryl
bromides and aryl chlorides are rarely used as cross-coupling
electrophiles. Even if they are used, harsh reaction conditions and
high catalyst loadings are usually needed. To overcome above
drawbacks, we need to develop more highly active catalytic
systems.
NH2
O
iPr
1)
i Pr
H
acetone
1)
2)
N
O
N
SeO
2
N
NH2
N
N
N
n
TMS-Cl,(HCHO)
2)
Cl
1
CO3
2
K
CuCl,
acetone
N-Heterocyclic carbenes (NHCs) are a class of effective and
N
N
versatile ligands owing to their strong σ-donor properties and
[14]
N
chemical robustness.
At present, a large number of NHC-Cu
Cu
Cl
complexes with different structures and properties have been
synthesized and since the first N-heterocyclic carbene copper
2
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Crystal of copper(I) complex
2
was grown by slow
Table 1. Optimization of the Ullmann coupling reactions of
p-nitrchlorobenzene with imidazole. a, c.
evaporation from a mixed CH2Cl2/petroleum ether solvent. The
molecular structure of complex 2 was determined by X-ray
single-crystal diffraction, as shown in Figure 1. Complex 2
crystallizes in the orthorhombic space group P212121, which is a
mononuclear structure containing one ligand, one CuI ion and one
Cl- anion. The CuI center is linked to one carbon atom (C1) of
carbene ligand and one Cl- ion (Cl1) to form nearly linear
Cl
2
mol%)
(1
base, solvent, 12 120 o
N
N
O2
N
NH
N
C
h,
NO2
3A
4a
5Aa
yield (%)c
o
entry
base
solvent
DMF
coordinated geometry (177.40(9) for the angle of C1-Cu1-Cl1).
K
2CO3
The bond angles for N1-C1-N2, N1-C1-Cu1 and N2-C1-Cu1 are
1
2
80
70
o
o
o
K2CO3
K2CO3
acetonitrile
102.6(2) , 131.7(2) and 125.8(2) , indicating that the Cl-Cu-C
unit is almost coplanar with the fused ring. No obvious Cu···N
contact is found. The bond lengths of Cu1-C1 and Cu1-Cl1 in
complex 2 are 1.869(3) and 2.1099(8) Å, respectively, which lie in
the expected range of CuI-C and CuI-N bonds.
3
4
5
6
3
1,4-dioxane
DMF/H
DMF/H
DMF/H
2O=2:1
2O=5:1
2O=10:1
K
10
20
40
2CO3
K2CO3
K2CO3
7b
8
9
10
11
12d
DMF
DMF
DMF
DMF
DMF
DMF
98
25
65
70
10
60
Cs2CO3
K3PO4
NaOH
KOH
t-BuOK
Cs2CO3
a Reactions were carried out using p-nitrchlorobenzene (0.2 mmol, 1 equiv),
imidazole (0.24 mmol, 1.2 equiv), 2 (0.002 mmol), base (0.4 mmol, 2 equiv)
in 0.4 mL solvent at 120 oC for 12 h. b Reaction was carried out for 0.5 h. c
Isolated yields. d Reaction was carried out for 0.5 h in the absence of
complex 2.
With the optimized conditions in hand, we started to explore
the substrate scope of the reaction. Representative
p-nitrchlorobenzene (3A) was chosen to react with various
N(H)-heterocycles (4) (Table 2). The reaction proceeded smoothly
with imidazole and an excellent yield (98%) was obtained. For
1,2,4-triazole and 4-methylimidazole, the reaction provided the
expected products 5Ab and 5Ad in high yield (85%). We were
pleased to discover that for hindered 2-methylimidazole also
could be coupled with p-nitrchlorobenzene in a good yield (80%).
Meanwhile, for high sterically hindered benzimidazole,
2,4-dimethylimidazole and 2-methylbenzimidazole, the desired
products (5Ae, 5Af and 5Ag) were obtained respectively in 70%,
88%, and 52% yields when the reaction time was delayed to 24 h.
Figure 1 Perspective view of copper(I) complex 2. Ellipsoids are drawn at
the 50% probability level. Selected interatomic distances (Å) and bond
angles (deg): C1-N1 = 1.355(3), C1-N2 = 1.369(3), C1-Cu1 = 1.869(3),
Cu1-Cl1
= 2.1099(8); N1-C1-N2 = 102.6(2), N1-C1-Cu1 = 131.7(2),
N2-C1-Cu1 = 125.8(2), C1-Cu1-Cl1 = 177.40(9).
The N-arylation reactions conditions of p-nitrchlorobenzene
with imidazole were screened, and the results are shown in Table
1. To optimize the reaction conditions, various bases and solvents
were investigated in the presence of copper(I) complex 2 (1 mol%)
o
at 120 C for 12 h. The effect of solvent on the coupling was first
examined. When single-solvent system (DMF or acetonitrile) was
used, moderate yields were obtained (80% and 70%, respectively)
(entries 1 and 2). But, when 1,4-dioxane was used as solvent, only
3% yield was obtained (entry 3). Mixed solvents of H2O with DMF
gave lower yields, 10-40% (entries 4-6). Therefore, with DMF as
solvent and K2CO3 as base, the highest yield was obtained (entry
1). The effect of different bases was also investigated and Cs2CO3
gave the best result (entries 7-11). In addition, a blank experiment
has been carried out in order to clarify the role of copper. The
result showed that only 60% yield was obtained in the absence of
complex 2 (entry 12).
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Running title
Chin. J. Chem.
Table 2. Catalytic activities of complex 2 in the N-arylation reactions of
p-nitrchlorobenzene with azoles under the optimized conditions. a, c.
imidazole, 1,2,3-triazole and 4-phenylimidazole worked well,
affording the desired products (6Ba, 6Bh and 6Bi) in high to
excellent yields (98%, 95% and 90%, respectively). The others
2
mol%)
(1
NO2
NO2
N
Het
Cl
Het-NH
N(H)-heterocycles
benzimidazole,
substrates,
hindered
including
2-methylimidazole
1,2,4-triazole,
and
Cs2CO3 DMF, 120 o
C
,
3A
4a-g
5
4-methylimidazole, also could couple with 2-chloroquinoline and
afforded the coupling products in good to high yields (80-88%).
2,4-Dimethylimidazole and 2-methylbenzimidazole gave moderate
yields (70% and 65%, respectively). When 2-chloroquinoline was
replaced by 2-chloropyridine derivatives with different functional
groups, such as 2-chloro-6-fluoropyridine, 2,6-dichloropyridine, or
2,5-dichloropyridine, they also successfully completed the
coupling with imidazole. The corresponding N-arylated products
(6Ca, 6Da and 6Ea, respactively) were also prepared in high to
excellent yields (85%, 80% and 95%, respectively).
N
O2N
N
O2N
N
O2N
N
N
N
N
5Aa
5Ab
5Ac
80%
,
98%
85%
,
,
O2N
N
O2N
N
N
N
O2N
N
N
70%b
88%b
5Af
,
5Ad
85%
,
5Ae
,
N
O2N
N
Conclusions
52%b
5Ag
,
In summary, a new N-heterocyclic carbene copper(I) complex
has been synthesized and used in the N-arylation of (hetero)aryl
chlorides and nitrogen heterocycles. With a low catalyst loading (1
mol %), both (hetero)aryl chlorides and N(H)-heterocycles
performed very well and a series of heteroarylazole derivatives
with high to excellent yields were obtained, which could be used
for the further preparation of industrially and pharmaceutically
important compounds. This new catalytic system provided an
important theoretical basis for the design of other catalytic
systems.
a Reactions were carried out using p-nitrchlorobenzene (0.2 mmol, 1 equiv),
azoles (0.24 mmol, 1.2 equiv), 2 (0.002 mmol), Cs2CO3 (0.4 mmol, 2 equiv)
in 0.4 mL DMF at 120 oC for 12 h. Reactions were carried out 24 h.
b
c
Isolated yields.
Table 3. Catalytic activities of complex 2 in the N-arylation reactions of
heteroaryl chlorides with azoles under the optimized conditions. a, b
2
mol%)
(1
+
Het
N
Het
Het-NH
Het-Cl
DMF, 12 120 o
Cs2CO3
C
,
h,
6
3B-E
4a-i
Experimental
Reagents and general techniques. Unless otherwise noted, all
reactions were performed under an atmosphere of dry N2 with
oven-dried glassware and anhydrous solvents. The reagents were
obtained from commercial sources and used directly.
1,8-Naphthyrido[1,2-a]-(2’,6’-diisopropylphenyl)limidazolium
chloride 1 was synthesized according to reference. [17]
N
N
N
N
N
N
N
N
N
N
N
6Ba
6Bh
6Bi
90%
,
98%
N
95%
,
,
N
N
N
N
N
Preparation of Cu(I)-NHC Complex 2: A suspension of CuCl
(14.3 mg, 0.144 mmol), K2CO3 (35.8 mg, 0.260 mmol) and
limidazolium chloride 1 (34.9 mg, 0.096 mmol) in dry acetone (2
mL) was heated at 60 oC for 24 h under a N2 atmosphere. After
cooling to room temperature, the solution was filtered and the
solvent was removed in vacuum. The residue was dissolved in
CH2Cl2, and then petroleum ether was added. The mixture was
filtered and the resulting yellow solid was washed with petroleum
ether and dried under vacuum. Yield: 60% (24.8 mg, 0.058 mmol).
Yellow solid. 1H NMR (400 MHz, CDCl3) δ (ppm): 8.80 (s, 1H), 8.13
(d, J = 4.0 Hz, 1H), 7.59-7.52 (m, 2H), 7.43-7.33 (m, 5H), 2.41 (m,
2H), 1.31 (d, J = 8.0 Hz, 6H), 1.18 (d, J = 8.0 Hz, 6H). 13C NMR (100
MHz, CDCl3) δ (ppm): 173.2, 147.8, 145.1, 144.5, 137.1, 135.4,
130.1, 129.2, 123.8, 123.2, 118.9, 116.9, 116.7, 28.1, 24.5, 24.0.
Anal. Calcd for C22H23ClCuN3: C, 61.67; H, 5.41; N, 9.81. Found:
C, 61.17; H, 5.38; N, 9.78.
N
N
N
6Bc
80%
,
6Bb
6Be
85%
,
88%
N
,
N
N
N
65%
N
N
N
N
N
N
6Bd
88%
,
6Bf
6Bg
70%
,
,
N
Cl
N
N
N
N
N
N
N
F
N
N
6Ca
6Da
6Ea
95%
,
85%
80%
,
,
a Reactions were carried out using heteroaryl chlorides (0.2 mmol, 1 equiv),
azoles (0.24 mmol, 1.2 equiv), 2 (0.002 mmol), Cs2CO3 (0.4 mmol, 2 equiv)
in 0.4 mL DMF at 120 oC for 12 h. b Isolated yields.
General Procedure for Cu(I)-NHC Catalyzed N-arylation of
(hetero)aryl chlorides with nitrogen heterocycles:
A test tube was charged with (hetero)aryl chlorides (0.2
mmol, 1 eq), nitrogen heterocycles (0.24 mmol, 1.2 eq), Cs2CO3
(0.4 mmol, 2 eq), DMF (0.4 mL) and complex 2 (0.002 mmol). The
Encouraged by the above results, the coupling reactions of a
variety of heteroaryl chlorides with azoles under the optimized
conditions were also investigated and the results were outlined in
Table 3. It is notable that the coupling of 2-chloroquinoline with
Chin. J. Chem. 2019, 37, XXX－XXX
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First author et al.
Report
mixture was heated at 120 oC for 12 h (or 24 h). After the reaction
was completed, the reaction mixture was cooled to room
temperature, diluted with dichloromethane (2 mL), washed with
water (3 x 2 mL). After removing the solvent under vacuum, the
resulting residue was purified by flash chromatography using a
mixture of hexane and ethyl acetate to provide the desired
products.
8.06 (d, J = 12.0 Hz, 1H), 7.89 (d, J = 8.0 Hz, 2H), 7.78 (t, J = 8.0 Hz,
1H), 7.59 (t, J = 8.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ (ppm):
147.9, 146.4, 139.6, 134.3, 130.7, 128.9, 127.9, 127.8, 127.1,
121.2, 112.7.
2-(4-Phenyl-imidazol-1-yl)-quinoline (6Bi): Yellow solid. Yield:
o
1
90%, mp 154-156 C. H NMR (400 MHz, CDCl3) δ (ppm): 8.49 (s,
1H), 8.23 (d, J = 8.0 Hz, 1H), 8.12 (s, 1H), 8.02 (d, J = 8.0 Hz, 1H),
7.90 (d, J = 8.0 Hz, 2H), 7.80 (d, J = 8.0 Hz, 1H), 7.74 (t, J = 8.0 Hz,
1H), 7.53-7.47 (m, 2H), 7.42 (t, J = 8.0 Hz, 2H), 7.29 (t, J = 8.0 Hz,
1H). 13C NMR (100 MHz, CDCl3) δ (ppm): 147.1, 146.8, 143.2,
139.5, 135.1, 133.4, 130.7, 128.6, 128.5, 127.5, 127.2, 126.8,
126.4, 125.0, 111.6, 111.3. Anal. Calcd for C18H13N3: C, 79.68; H,
1-(4-Nitro-phenyl)-1H-imidazole (5Aa): [13e] Yellow solid. Yield:
98%. 1H NMR (400 MHz, DMSO) δ (ppm): 8.49 (s, 1H), 8.34 (d, J =
12.0 Hz, 2H), 7.96 (d, J = 8.0 Hz, 2H), 7.93 (s, 1H), 7.18 (s, 1H). 13
C
NMR (100 MHz, DMSO) δ (ppm): 145.3, 141.8, 136.1, 130.9,
125.6, 120.4, 118.0.
[18]
1-(4-Nitro-phenyl)-1H-[1,2,4]triazole (5Ab):
White solid.
4.83; N, 15.49. Found: C, 79.71; H, 4.69; N, 15.61.
1
[19]
Yield: 85%. H NMR (400 MHz, CDCl3) δ (ppm): 8.71 (s, 1H), 8.40
2-[1,2,4]Triazol-1-yl-quinoline (6Bb):
White solid. Yield:
(d, J = 8.0 Hz, 2H), 8.16 (s, 1H), 7.92 (d, J = 8.0 Hz, 2H). 13C NMR
88%. H NMR (400 MHz, CDCl3) δ (ppm): 9.34 (s, 1H), 8.27 (d, J =
8.0 Hz, 1H), 8.12 (s, 1H), 8.03-7.97 (m, 2H), 7.81 (d, J = 8.0 Hz, 1H),
7.74-7.70 (m, 1H), 7.54-7.50 (m, 1H). 13C NMR (100 MHz, CDCl3) δ
(ppm): 152.6, 147.7, 146.0, 141.6, 139.4, 130.5, 128.4, 127.5,
1
(100 MHz, CDCl3) δ (ppm): 153.5, 146.8, 141.3, 125.6, 119.9.
[13i]
2-Methyl-1-(4-nitro-phenyl)-1H-imidazole (5Ac):
Yellow
1
solid. Yield: 80%. H NMR (400 MHz, CDCl3) δ (ppm): 8.34 (d, J =
12.0 Hz, 2H), 7.88 (s, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.09 (s, 1H), 2.29
(s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 145.8, 142.0, 141.0,
134.4, 125.7, 120.3, 113.8, 13.7.
127.3, 126.6, 111.9.
[19]
2-Benzoimidazol-1-yl-quinoline (6Be):
Yellow solid. Yield:
1
85%. H NMR (400 MHz, CDCl3) δ (ppm): 8.68 (s, 1H), 8.42 (d, J =
8.0 Hz, 1H), 8.14 (d, J = 12.0 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.98
(d, J = 8.0 Hz, 1H), 7.75-7.71 (m, 2H), 7.51-7.45 (m, 4H). 13C NMR
(100 MHz, CDCl3) δ (ppm): 148.0, 146.5, 144.3, 140.8, 138.8,
131.8, 130.2, 128.1, 127.1, 125.9, 124.0, 123.1, 120.1, 113.7,
112.2.
4-Methyl-1-(4-nitro-phenyl)-1H-imidazole (5Ad): Yellow solid.
o
1
Yield: 85%, mp 144-146 C. H NMR (400 MHz, CDCl3) δ (ppm):
8.32 (d, J = 8.0 Hz, 2H), 7.87 (s, 1H), 7.52 (d, J = 12.0 Hz, 2H), 7.08
(s, 1H), 2.28 (s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 145.7,
142.0, 141.0, 134.4, 125.6, 120.3, 113.8, 13.6. Anal. Calcd for
C10H9N3O2: C, 59.11; H, 4.46; N, 20.68. Found: C, 59.37; H, 4.52;
2-(2-Methyl-imidazol-1-yl)-quinoline (6Bc): Yellow solid. Yield:
80%, mp 68-70 oC. 1H NMR (400 MHz, CDCl3) δ (ppm): 8.27 (d, J =
8.0 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H),
7.77-7.73 (m, 1H), 7.58-7.54 (m, 1H), 7.43 (d, J = 12.0 Hz, 1H), 7.39
(d, J = 4.0 Hz, 1H), 7.06 (d, J = 4.0 Hz, 1H), 2.71 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ (ppm): 149.2, 146.7, 145.3, 139.1, 130.5,
128.8, 128.0, 127.4, 126.8, 126.5, 118.7, 115.4, 15.7. Anal. Calcd
for C13H11N3: C, 74.62; H, 5.30; N, 20.08. Found: C, 74.66; H,
5.37; N, 19.98.
N, 20.55.
[18]
1-(4-Nitro-phenyl)-1H-benzoimidazole (5Ae):
Yellow solid.
1
Yield: 70%. H NMR (400 MHz, DMSO) δ (ppm): 8.72 (s, 1H), 8.42
(d, J = 12.0 Hz, 2H), 7.99 (d, J = 8.0 Hz, 2H), 7.80 (d, J = 8.0 Hz, 1H),
7.74 (d, J = 8.0 Hz, 1H), 7.39-7.32 (m, 2H). 13C NMR (100 MHz,
DMSO) δ (ppm): 145.7, 144.2, 143.3, 141.4, 132.4, 125.6, 124.1,
123.7, 123.2, 120.3, 111.0.
2,4-Dimethyl-1-(4-nitro-phenyl)-1H-imidazole (5Af): Yellow
o
1
solid. Yield: 88%, mp 184-186 C. H NMR (400 MHz, CDCl3) δ
(ppm): 8.34 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 12.0 Hz, 2H), 6.78 (s,
1H), 2.40 (s, 3H), 2.23 (s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm):
146.4, 143.6, 143.2, 137.8, 125.7, 125.3, 125.0, 120.3, 116.3, 14.1,
13.3. Anal. Calcd for C11H11N3O2: C, 60.82; H, 5.10; N, 19.34.
Found: C, 60.77; H, 5.09; N, 19.29.
2-(4-Methyl-imidazol-1-yl)-quinoline (6Bd): Yellow solid.
o
1
Yield: 88%, mp 90-92 C. H NMR (400 MHz, CDCl3) δ (ppm): 8.40
(s, 1H), 8.23 (d, J = 12.0 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.79 (d, J =
8.0 Hz, 1H), 7.74-7.70 (m, 1H), 7.55 (s, 1H), 7.52-7.49 (m, 1H), 7.43
(d, J = 8.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ (ppm): 147.5,
146.9, 139.4, 130.6, 128.6, 127.5, 126.7, 126.2, 111.5, 13.7. Anal.
Calcd for C13H11N3: C, 74.62; H, 5.30; N, 20.08. Found: C, 74.71;
H, 5.31; N, 20.00.
2-Methyl-1-(4-nitro-phenyl)-1H-benzoimidazole (5Ag): Yellow
o
1
solid. Yield: 52%, mp 226-228 C. H NMR (400 MHz, CDCl3) δ
(ppm): 8.48 (d, J = 12.0 Hz, 2H), 7.77 (d, J = 8.0 Hz, 1H), 7.62 (d, J =
8.0 Hz, 2H), 7.34-7.24 (m, 2H), 7.18 (d, J = 8.0 Hz, 1H), 2.58 (s, 3H).
13C NMR (100 MHz, CDCl3) δ (ppm): 150.7, 147.2, 142.7, 141.6,
135.5, 127.5, 125.4, 123.2, 123.1, 119.4, 109.5, 14.6. Anal. Calcd
for C14H11N3O2: C, 66.40; H, 4.38; N, 16.59. Found: C, 66.32; H,
4.27; N, 16.61.
2-(2,4-Dimethyl-imidazol-1-yl)-quinoline (6Bf): Yellow solid.
o
1
Yield: 70%, mp 95-97 C. H NMR (400 MHz, CDCl3) δ (ppm): 8.26
(d, J = 8.0 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H),
7.77-7.73 (m, 1H), 7.58-7.54 (m, 1H), 7.41 (d, J = 8.0 Hz, 1H), 7.12
(s, 1H), 2.69 (s, 3H), 2.26 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
(ppm): 149.3, 146.9, 144.7, 139.0, 137.0, 130.5, 128.8, 127.4,
126.7, 126.5, 115.4, 114.8, 15.8, 13.4. Anal. Calcd for C14H13N3:
C, 75.31; H, 5.87; N, 18.82. Found: C, 75.24; H, 5.86; N, 18.92.
2-(2-Methyl-benzoimidazol-1-yl)-quinoline (6Bg): Yellow
2-Imidazol-1-yl-quinoline (6Ba): [4g] White solid. Yield: 98%. 1H
NMR (400 MHz, CDCl3) δ (ppm): 8.49 (s, 1H), 8.25 (d, J = 8.0 Hz,
1H), 8.01 (d, J = 8.0 Hz, 1H), 7.82-7.80 (m, 2H), 7.76-7.71 (m, 1H),
7.54-7.51 (m, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.24 (s, 1H). 13C NMR
(100 MHz, CDCl3) δ (ppm): 146.8, 139.5, 130.7, 128.6, 127.5,
o
1
solid. Yield: 65%, mp 365-367 C. H NMR (400 MHz, CDCl3) δ
(ppm): 8.39 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.93 (d, J =
8.0Hz, 1H), 7.83-7.79 (m, 1H), 7.77 (d, J = 8.0 Hz, 1H) 7.66-7.62 (m,
1H), 7.59 (d, J = 12.0 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.32-7.22 (m,
2H), 2.77 (s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 149.2, 146.7,
126.8, 126.4, 111.6.
[19]
2-[1,2,3]Triazol-1-yl-quinoline (6Bh):
Yellow solid. Yield:
95%. 1H NMR (400 MHz, CDCl3) δ (ppm): 8.82 (s, 1H), 8.37 (s, 2H),
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Running title
Chin. J. Chem.
145.3, 139.1, 130.5, 128.8, 128.7, 128.0, 127.4, 126.8, 126.5,
118.7, 115.4, 15.7. Anal. Calcd for C17H13N3: C, 78.74; H, 5.05; N,
16.20. Found: C, 78.76; H, 5.01; N,16.17.
W. Modern Synthetic Methods for Copper-Mediated C(aryl)-O,
C(aryl)-N, and C(aryl)-S Bond Formation. Angew. Chem., Int. Ed., 2003,
42, 5400-5449; (b) Beletskaya, I. P.; Cheprakov, A. V. Copper in
Cross-Coupling Reactions: The Post-Ullmann Chemistry. Coord. Chem.
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Formation. Angew. Chem., Int. Ed., 2017, 56, 16136-16179.
2-Fluoro-6-imidazol-1-yl-pyridine (6Ca): [20] Yellow solid. Yield:
1
85%. H NMR (400 MHz, CDCl3) δ (ppm): 8.36 (s, 1H), 7.81 (t, J =
8.0 Hz, 1H), 7.65 (s, 1H), 7.32-7.28 (m, 2H), 7.22 (s, 1H). 13C NMR
(100 MHz, CDCl3) δ (ppm): 150.6, 148.6, 141.2, 134.9, 130.9,
122.1, 116.0, 110.2. 19F NMR (376 MHz, CDCl3) δ (ppm): -66.20.
[20]
2,6-Di-imidazol-1-yl-pyridine (6Da):
Yellow solid. Yield:
1
80%. H NMR (400 MHz, CDCl3) δ (ppm): 8.41 (s, 2H), 8.00 (t, J =
8.0 Hz, 1H), 7.70 (s, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.26 (s, 2H). 13C
NMR (100 MHz, CDCl3) δ (ppm): 148.2, 142.0, 134.9, 131.0, 116.0,
109.5.
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5-Chloro-2-imidazol-1-yl-pyridine (6Ea): Yellow solid. Yield:
95%, mp 127-129 oC. 1H NMR (400 MHz, CDCl3) δ (ppm): 8.39 (d, J
= 2.3 Hz, 1H), 8.28 (s, 1H), 7.76 (dd, J = 8.7 Hz, 2.5 Hz, 1H), 7.56 (s,
1H), 7.29 (d, J = 8.0 Hz, 1H), 7.17 (s, 1H). 13C NMR (100 MHz,
CDCl3) δ (ppm): 147.7, 147.2, 138.6, 134.8, 130.8, 129.5, 116.0,
112.9. Anal. Calcd for C8H6ClN3: C, 53.50; H, 3.37; N, 23.40.
Found: C, 53.71; H, 3.27; N, 23.32.
Supporting Information
NMR spectra of complex 2 and all products. CCDC 1964792
contain the supplementary crystallographic data for complex 2.
This data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html,
or
from
the
S.;
Ma,
D.
Copper(I)
Coupling of
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
Oxide/N,N’-Bis[(2-furyl)methyl]oxalamide-Catalyzed
(Hetero)aryl Halides and Nitrogen Heterocycles at Low Catalytic
Loading. Adv. Synth. Catal., 2017, 359, 1631-1636.
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Copper-Catalyzed Coupling of Aryl Halides with Imidazoles.
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Copper Catalysed Aromatic N-arylation In Water. Green Chem., 2013,
15, 336-340; (e) Zhao, Y.; Wang, X.; Kodama, K.; Hirose, T.
Copper-Catalyzed Coupling Reactions of Aryl Halides and Phenols by
Acknowledgement
This work was supported by the Natural Science Foundation of
Tianjin (No. 16JCYBJC19700), and the National Natural Science
Foundation of China (No. 21771138).
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Running title
Chin. J. Chem.
Entry for the Table of Contents
Page No.
N-Heterocyclic Carbene Copper(I) Complex Catalyzed
Coupling of (Hetero)aryl Chlorides and Nitrogen
Heterocycles: Highly Efficient Catalytic System
A highly efficient NHC-copper(I) complex was developed. The structure of this NHC-copper(I)
complex has been determined by X-ray crystallography. This NHC-copper(I) complex was found to
be efficient for the N-arylation reactions of (hetero)aryl chlorides and nitrogen Heterocycles with
low catalyst loading.
Mengyao Zhang, Yingying Zhang, Huixin Zhang,
Yongfei Zeng*, Guiyan Liu*
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
This article is protected by copyright. All rights reserved.