Chan–Lam cross-coupling reactions promoted by anionic copper(I)/iodide species with cationic methyl-((pyridinyl)-pyrazolyl)pyridin-1-ium

Article abstract of DOI:10.1016/j.tet.2016.09.032

Four anionic ligands including 1-methyl-3(or 4)-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-ium iodide ([3,2′-pypzpym]I, [4,2′-pypzpym]I) and 1-methyl-3(or 4)-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)pyridin-1-ium iodide ([2,3′-pypzpym]I, [2,4′-pypzpym]I) are prepared. Reaction of CuI with [3,2′-pypzpym]I affords a mononuclear complex [CuI₂(3,2′-pypzpym)] (1) and a one-dimensional coordination polymer [(Cu₄I₆)(3,2′-pypzpym)₂]_n(2). Analogous reactions of CuI with [4,2′-pypzpym]I, [2,3′-pypzpym]I or [2,4′-pypzpym]I yield [Cu₄I₆(4,2′-pypzpym)₂] (3), [CuI₂(2,3′-pypzpym)] (4) and [CuI₂(2,4′-pypzpym)] (5), respectively. Relative to that of CuI, complexes 1–5 exhibit enhanced catalytic activities towards the Chan–Lam cross-coupling reactions of imidazole and arylboronic acids in a H₂O[sbnd]MeCN (v/v=2:1). This catalytic system is involved in the C[sbnd]N cross-coupling reaction and works for a variety of imidazole derivatives as well as arylboronic acids with different electronic properties.

Full text of DOI:10.1016/j.tet.2016.09.032

Accepted Manuscript
Chan-Lam cross-coupling reactions promoted by anionic copper(I)/iodide species with
cationic methyl-((pyridinyl)-pyrazolyl)pyridin-1-ium
Jiang-Yan Xue, Jun-Chi Li, Hong-Xi Li, Hai-Yan Li, Jian-Ping Lang
PII:
S0040-4020(16)30948-6
10.1016/j.tet.2016.09.032
TET 28103
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 7 August 2016
Revised Date: 11 September 2016
Accepted Date: 18 September 2016
Please cite this article as: Xue J-Y, Li J-C, Li H-X, Li H-Y, Lang J-P, Chan-Lam cross-coupling reactions
promoted by anionic copper(I)/iodide species with cationic methyl-((pyridinyl)-pyrazolyl)pyridin-1-ium,
Tetrahedron (2016), doi: 10.1016/j.tet.2016.09.032.
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Chan-Lam cross-coupling reactions
promoted by anionic copper(I)/iodide species
with cationic methyl-((pyridinyl)-
pyrazolyl)pyridin-1-ium
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Jiang-Yan Xue , Jun-Chi Li , Hong-Xi Li ∗ , Hai-Yan Li , Jian-Ping Lang ∗
a
State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of
Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
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Tetrahedron
journal homepage: www.elsevier.com
Chan-Lam cross-coupling reactions promoted by anionic copper(I)/iodide species
with cationic methyl-((pyridinyl)-pyrazolyl)pyridin-1-ium
a
a
a
a
a,b
Jiang-Yan Xue , Jun-Chi Li , Hong-Xi Li ∗ , Hai-Yan Li , Jian-Ping Lang ∗
a
State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science,
Soochow University, Suzhou 215123, P. R. China
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 210032, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Four anionic ligands including 1-methyl-3(or 4)-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-
ium iodide ([3,2'-pypzpym]I, [4,2'-pypzpym]I) and 1-methyl-3(or 4)-(3-(pyridin-2-yl)-1H-
pyrazol-1-yl)pyridin-1-ium iodide ([2,3'-pypzpym]I, [2,4'-pypzpym]I) are prepared. Reaction of
CuI with [3,2'-pypzpym]I affords a mononuclear complex [CuI
dimensional coordination polymer [(Cu )(3,2'-pypzpym) (2). Analogous reactions of CuI
with [4,2'-pypzpym]I, [2,3'-pypzpym]I or [2,4'-pypzpym]I yield [Cu (4,2'-pypzpym) ] (3),
CuI (2,3'-pypzpym)] (4) and [CuI (2,4'-pypzpym)] (5), respectively. Relative to that of CuI,
complexes 1-5 exhibits enhanced catalytic activities towards the Chan-Lam cross-coupling
reactions of imidazole and arylboronic acids in a H O-MeCN (v/v = 2:1). This catalytic system
2
(3,2'-pypzpym)] (1) and a one-
Available online
4
I
6
2 n
]
4
I
6
2
[
2
2
Keywords:
Chan-Lam cross-coupling
Copper
2
is involved in the C-N cross-coupling reaction and works for a variety of imidazole derivatives
as well as arylboronic acids with different electronic properties.
N-alkylation
Arylboronic acid
Aqueous MeCN
Water-soluble
2009 Elsevier Ltd. All rights reserved.
1
. Introduction
N-aryl heterocycles have attracted increasing attention due to
in water with relatively low yields (up to 63%). It is noted that
water-soluble catalysts could be obtained by incorporating
hydrophilic moieties such as sulfonate, carboxylate, imidazolium
salts, ammonium groups into the hydrophobic organic ligands.
As our continuous effort on the syntheses of water-soluble metal
their wide applicability in biochemical, biological, medicinal and
material sciences. The most straightforward routes for synthesis
of N-arylazole derivatives involve copper-mediated Ullmann-
type coupling and Pd-catalyzed Buchwald-Hartwig reaction of
nitrogen-containing heterocycles with aryl halides. These
reactions require expensive catalysts, or hard reaction conditions
1
10
11
coordination complexes and the formation of C-N bond, we
have designed and prepared a set of N,N-bidentate coordination
ligands attached 1-methyl-pyridinium group (1-methyl-
2
3
((pyridinyl)pyrazolyl)pyridin-1-ium
iodide
([pypzpym]I))
(such as high reaction temperature) and produce large amount of
(Scheme 1). Reactions of CuI with these ligands afforded five
4
harmful wastes. Since 1998, the Chan-Lam coupling reaction
has emerged as a highly efficient and valuable alternative to
traditional methods for the construction of C-N bond due to the
wide variety of commercially available boronic acids and the
anionic [Cu I ]-based coordination complexes [CuI (3,2'-
x y
2
pypzpym)] (1), [Cu I ] [(3,2'-pypzpym) ] (2), [Cu I (4,2'-
4
6 n
2n
4 6
pypzpym) ] (3), [CuI (2,3'-pypzpym)] (4) and [(CuI )(2,4'-
2
2
2
pypzpym)] (5). Compared with that of CuI, complexes 1-5
displayed greatly enhanced catalytic activities toward the
5
mildness of the reaction conditions. These reactions are often
6
7
carried out in organic solvents or ionic liquids. It would be a
greener and more economic approach if the Chan-Lam coupling
reaction could be conducted in water or aqueous solvents.
Recently, a number of green water-soluble catalysts have been
coupling of imidazole with arylboronic acid in H O/MeCN (v/v =
2
2
:1). Described below are their syntheses, crystal structures and
catalytic properties.
8
used to promote C−C cross-coupling reactions in water. So far,
2. Results and discussion
the homogeneous copper-catalyzed Chan-Lam cross-coupling9
12
According to the literature, reactions of 3-/4-(1H-pyrazol-3-
yl)-pyridine with 2-iodopyridine or 2-(1H-pyrazol-3-yl)pyridine
with 3-iodopyridine or 4-iodopyridine produced 2-(3-(pyridin-3-
systems in water or in aqueous solvents have less explored.
Collman et al. reported that [Cu(OH)·TMEDA] Cl2 could
2
catalyze coupling reactions of imidazole with arylboronic acids
—
——
∗
∗
Corresponding author. Tel.: +86-512-6588-3569; e-mail: lihx@suda.edu.cn
Corresponding author. Tel.: +86-512-6588-2865; fax: +86-512-6588-0328; e-mail: jplang@suda.edu.cn
2

yl)-1H-pyrazol-1-yl)pyridine (3,2’-pypzpy), 2-(3-(pyridin-4-yl)-
aggregates. On the other end, the pyridyl and pyrazol groups in 1,
3 and 4 work together to chelate one Cu center in a N,N’-
ACCEPTED MANUSCRIPT
1
H-pyrazol-1-yl)pyridine (4,2’-pypzpy), 2-(1-(pyridin-3-yl)-1H-
pyrazol-3-yl)pyridine (2,3’-pypzpy) and 2-(1-(pyridin-4-yl)-1H-
pyrazol-3-yl)pyridine (2,4’-pypzpy), respectively. As shown
Scheme 1, reactions of 3,2’-pypzpy, 4,2’-pypzpy, 2,3’-pypzpy or
bidentate coordination fashion.
Being crystallized in the monoclinic space group P2 /n, the
asymmetric unit of 1 or 4 contains the discrete molecule
1
2
1
,4’-pypzpy with excess MeI in refluxing THF for 12 h produced
-methyl-3(or 4)-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-
[
CuI (3,2'-pypzpym)] or [CuI (2,3'-pypzpym)]. Their cell
2
2
parameters are essentially identical, and so are their molecular
structures (Fig. 1 and Fig. S1). Therefore only the molecular
structure of 1 is described below. Each Cu(I) in 1 is tetrahedrally
coordinated by two I and two N atoms from 3,2'-pypzpym ligand.
Compound 2 crystallizes in the triclinic space group Pī, and its
asymmetric unit contains [Cu I ] anion and one 3,2'-pypzpym
cation. As shown in Fig. 2, I(1) atom bridges four Cu(I) atoms.
The two adjacent Cu(I) atoms are further connected by ꢀ-I ion,
forming a pyramid-shaped structure. Such [Cu
ium iodide ([3,2'-pypzpym]I, [4,2'-pypzpym]I) and 1-methyl-3(or
)-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)pyridin-1-ium iodide ([2,3'-
4
pypzpym]I, [2,4'-pypzpym]I) in high yields. These four organic
1
ligands were fully characterized by elemental analysis, IR, H
13
and C NMR spectroscopy, and mass spectrometry. Their high-
resolution positive-ion mass spectra reveal that there exists one
peak at m/z = 237.1142 ([3,2'-pypzpym]I, [4,2'-pypzpym]I),
-
2
3
-
2
37.1140 ([2,3'-pypzpym]I) and 237.1146 ([2,4'-pypzpym]I),
+
4
I
5
] unit shares two
which can be assigned to the corresponding [pypzpym] cation.
These cationic ligands are stable toward air and moisture, and
freely soluble in H O, MeOH, DMSO, slightly soluble in CH Cl
“
[Cu I ]” rhomboids with two adjacent ones to form an infinite
2
2
2n-
1
D anionic ribbon [Cu (ꢀ -I) (ꢀ-I) ]
4 n
running parallel to the a
4
4
2
2
2
2
axis. Compound 3 crystallizes in the triclinic space group Pī, and
its asymmetric unit has half a discrete molecule [Cu I (4,2'-
and CHCl , but insoluble in toluene and Et O.
3
2
4
6
pypzpym)2]. It may be viewed as having
a chairlike
N
[{Cu(CuI)}(ꢀ-I)(ꢀ -I)] core structure (Fig. 3). All Cu(I) centers
3
2
N
N
I-
N
in 3 are tetrahedrally coordinated by one ꢀ-I, one ꢀ -I and two N
atoms of 4,2'-pypzpym and (Cu1 or Cu1A), or by one I, one ꢀ-I
N
3
N
N
N+
(
3,2'-pypzpy)
(
[3,2'-pypzpym]I)
and two ꢀ -I atoms (Cu2 or Cu2A).
3
N
N
N
N
I
-
N
N
N+
N
(
4,2'-pypzpy)
CH
3
I
(
[4,2'-pypzpym]I)
THF
N
N
N
N
I-
N
N+
N
N
(2,3'-pypzpy)
([2,3'-pypzpym]I)
N
N
N
I-
N+
N
N
N
N
(2,4'-pypzpy)
([2,4'-pypzpym]I)
Fig. 1 View of the molecular structure of
1
with a labeling scheme and
50% thermal ellipsoids. All H atoms are omitted for clarity.
Scheme 1 Synthesis of [pypzpym]I ligands.
Diffusion of Et O into the MeCN solution containing CuI and
2
[
[
[
3,2'-pypzpym]I afforded red crystals of mononuclear complex
CuI (3,2'-pypzpym)] (1) and yellow crystals of 1D polymer
2
(Cu I )(3,2'-pypzpym) ] (2) in 23 % and 35 % yields,
4
6
2 n
respectively. The similar reaction in refluxing MeCN only
produced 1 in a higher yield (88%). Refluxing of the MeCN
solution of 2 could also produce complex 1. Reactions of CuI
with [4,2'-pypzpym]I, or [2,3'-pypzpym]I or [2,4'-pypzpym]I in
MeCN at room temperature resulted in the formation of one
tetranuclear Cu(I) cluster [Cu I (4,2'-pypzpym) ] (3) and two
4
6
2
mononuclear complexes [CuI (2,3'-pypzpym)] (4) and
2
[
(CuI )(2,4'-pypzpym)] (5), respectively. Compounds 1–5 are
2
also relatively air and moisture-stable. They are soluble in
common organic solvents such as CH Cl , MeOH, EtOH and
2
2
MeCN, DMF, DMSO and H O, but insoluble in Et O and n-
2
2
hexane. The elemental analyses are consistent with their
chemical formula. Their identities of 1-4 are finally confirmed by
single-crystal X-ray crystallography. Numerous attempts to grow
crystals of 5 always failed. As described below in this article, the
sites of pyridinium group in pypzpym ligands have a significant
(
y-x)-
influence on the anionic [Cu X ]
structural motifs such as
x
y
-
2-
monomeric unit [CuI ] in 1 and 4, chair-like unit [Cu I ] in 3
and ribbon chain [Cu I ] in 2. For the pypzpym ligands in 1-4,
2
4 6
2n-
4
6 n
2n-
Fig. 2 View of the 1D [Cu
4
(ꢀ
4
-I)
2
(ꢀ-I)
4
]
n
chain in 2 with a labeling scheme
the cationic part on one end of its backbone is used to balance the
and 50% thermal ellipsoids. All H atoms are omitted for clarity.
-
2-
2n-
anionic charges for anionic [CuI ] , [Cu I ] and [Cu4I6]n
2
4 6
3

hydropholic aryl group, the aqueous organic solvent mixtures
ACCEPTED MANUSCRIPT
may be more suitable for such a cross-coupling reaction. When
the reaction was carried out in a H O-MeCN (v/v = 1:1) mixture,
2
the isolated yield of 8a was increased dramatically (89%, entry
3
). However, this catalyst showed slightly lower activity in
aqueous DMF, DMSO, MeOH, EtOH (entries 4-7). The reaction
temperature also exerted great impact on this reaction. At lower
temperature (40 ºC) or higher temperature (80 ºC), the reaction
gave the product in lower yields (entries 8 and 9). As shown in
Table 1, the optimal ratio of H O and MeCN was finally
2
determined to be 2 : 1 (entries 10-12). A blank experiment
confirmed that no arylated product was observed in the absence
of the catalyst (entry 13). Notably, the catalyst loading for this
reaction could be increased from 2 to 5 mol% without affecting
the product yields (entry 15). When the catalyst loading was
reduced to 1 mol%, it gave the product in lower yields (entry 14).
Based on these results, the optimized reaction conditions were
Fig. 3 View of the molecular structure of 3 with a labeling scheme and
0% thermal ellipsoids. All H atoms are omitted for clarity.
5
Since complexes 1-5 can dissolve in water, they may show
high catalytic activity towards some reactions in H O. To this end,
2
we examined the catalytic activity of the as-synthesized Cu(I)
complexes for the Chan–Lam coupling reaction. The initial
experiment was performed by stirring a mixture of imidazole (6a,
fixed to be 2 mol% of 1, at 60 ºC in H O-MeCN (v/v = 2:1) for
2
2
4
h. Under these optimized conditions, the catalytic
performances of 2-5 and CuI/[3,2'-pypzpym]I were also
investigated. They also exhibited good catalytic activity towards
the cross-coupling reaction of 1H-Imidazole with phenylboronic
acid to 1-phenyl-1H-imidazole (85-90%, entries 16-20). As
1
mmol), phenylboronic acid (7a, 2 mmol) and 1 (0.02 mmol) in
H O at 60 ºC. After 24 hours, the desired product 1-phenyl-1H-
2
imidazole (8a) could be isolated in 65% yield (Table 1, entry 1).
This preliminary result suggested that 1 could initialize the N-
discussed above,
2
could be transformed into "(3,2'-
arylation of imidazole. The relatively low yield showed that H O
2
pypzpym)Cu" active catalytic species in the catalytic process.
Comparative run with CuI (67 %) catalytic system under the
same reaction conditions indicated that 1-5 exhibited better
catalytic performance (entry 20).
may not be the optimal solvent. When the reaction was carried
out in MeCN, only the coupling product 1,1'-biphenyl (9a) was
isolated in 58% (entry 2). Considering the structure of
arylboronic acid containing the hydrophilic boronic acid and the
Table 1. Optimizing the reaction conditions for the cross-coupling reaction of 1H-Imidazole with phenylboronic acid.
cat.
N
N
NH +
B(OH)2
N
+
solvent, T
6
a
7a
8a
9a
a
b
b
Entry
Cat.
[Cu] Loading (mol%)
Solvent
Temp (ºC)
60
Yield of 8a (%)
Yield of 9a (%)
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
1
1
-
2
2
2
2
2
2
2
2
2
2
2
2
-
H
2
O
65
trace
89
84
79
83
81
43
78
91
87
82
-
-
MeCN
60
58
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
O/MeCN (1:1)
O/MeOH (1:1)
O/EtOH (1:1)
O/DMF (1:1)
O/DMSO (1:1)
O/MeCN (1:1)
O/MeCN (1:1)
O/MeCN (2:1)
O/MeCN (3:1)
O/MeCN (4:1)
O/MeCN (2:1)
O/MeCN (2:1)
O/MeCN (2:1)
O/MeCN (2:1)
O/MeCN (2:1)
O/MeCN (2:1)
O/MeCN (2:1)
O/MeCN (2:1)
O/MeCN (2:1)
60
-
60
trace
60
trace
60
trace
60
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
40
80
1
1
1
1
1
1
1
1
1
1
2
2
0
1
2
3
4
5
6
7
8
9
0
1
60
60
60
60
1
1
2
3
4
5
1
5
2
2
2
2
2
2
60
82
90
90
90
85
87
88
67
60
60
60
60
60
CuI/[3,2'-pypzpym]I
60
CuI
60
a
Reaction conditions: phenylboronic acid (2.0 mmol), imidazole (1.0 mmol), solvent (4.0 ml) in O
Isolated yield.
2
for 24h.
b
4

ACCEPTED MANUSCRIPT
Table 2. Reaction of 1H-imidazole with various arylboronic acids.
R1
R1
N
1
(2 mol%), 60 o
MeCN/H O (1/2)
C
HN
N
+
B(OH)
2
N
R2
2
R2
6
7
8
a
b
Entry
nitroarene
alcohol
product
Yield (%)
1
6a
OH
B
7a
N
N
8a
91
N
NH
OH
OH
B
OH
2
3
4
6a
6a
6a
7b
7c
7d
N
N
8b
8c
8d
95
92
87
N
N
N
NH
NH
NH
O
O
OH
N
N
B
OH
OH
OH
N
N
B
5
6a
7e
8e
81
N
NH
OH
B
N
N
OH
OH
B
OH
6
7
8
6a
6a
6a
7f
N
N
8f
74
63
87
N
N
N
NH
NH
NH
F
3
C
CF3
OH
7g
7h
N
N
8g
8h
O N
B
NO
2
2
OH
OH
OH
N
N
B
9
1
6a
6b
7i
8i
8j
85
83
N
NH
OH
OH
N
N
B
0
1
N
OH
OH
7a
B
N
N
N
H
1
1
N
6c
OH
OH
7a
7a
8k
8l
85
86
B
N
H
N
N
2
N
6d
OH
OH
N
B
N
N
H
N
OH
B
OH
OH
B
N
N
1
1
3
4
6e
6f
7a
7a
8m
8n
90
55
NH
H
NH2
N
OH
1
5
NH2
6g
OH
OH
7a
8o
15
B
HN
O
O
a
b
Reaction conditions: imidazole (1.0 mmol), arylboronic acid (2.0 mmol), H
2 2
O/MeCN (2/1) (4.0 ml), 1 atm O and 2 mol% 1 at 60 ºC for 24 h.
Isolated yield.
With the optimized reaction conditions in hand, a variety of
products were isolated in moderate to excellent yields (entries 1-
9). The electronic nature of substituents on phenylboronic acid
had some effects on such a cross-coupling reaction. As shown in
Table 2, electron-donating p-substituted arylboronic acids were
found to proceed in higher yields than those with electron-
arylboronic acids were chosen as the substrates in this cross-
coupling reaction. As demonstrated in Table 2, the cross-
coupling reactions of 1H-imidazole with arylboronic acids were
performed well for all the substrates examined, and the desired
5

deficient substituent groups. For example, the p-methyl, p-
methoxyphenylboronic acids were converted smoothly into 1-(p-
tolyl)-1H-imidazole and 1-(4-methoxyphenyl)-1H-imidazole in
and 4 are used as both counter ion and chelating ligand. It seems
ACCEPTED MANUSCRIPT
that the structure of pypzpym ligands has exerted a significant
(
y-x)-
-
influence on the [CuxIy]
motifs such as monnuclear [CuI ]
2
2-
9
2% and 95% yields, respectively (entries 2 and 3).
unit in 1 and 4, chair-like unit [Cu I ] in 3 and 1D ribboned
chain [Cu I ] in 2. In comparison with that of CuI, complexes
4 6 n
4
6
2n-
Phenylboronic acids ((4-(trifluoromethyl)phenyl)boronic acid, 1-
nitro-4-(trifluoromethyl)benzene) with electron-withdrawing
substituents like -CF and -NO could proceed conveniently, in
1-5 display highly improved catalytic activity toward the Chan-
Lam cross-coupling of 1H-imidazole with various arylboronic
acids in aqueous MeCN to produce the corresponding N-
arylimidazoles with high yields. It is anticipated that the new
cationic/anionic N-coordinating ligands may be applied in other
3
2
7
4% and 63% yields (entries 6 and 7). It seemed that 3-
substituent on phenyl ring of phenylboronic acid did not hamper
the N-arylation reaction (87%, entry 4). o-Tolylboronic acid with
higher steric hindrance was also converted into its corresponding
[Cu I ]-based coordination complexes with better catalytic
x y
1
-o-tolyl-1H-imidazole in good yield (81%, entry 5). We also
properties. Studies in this respect are underway in our laboratory.
examined the scope of the substrate imidazole derivatives. As
shown in Table 2, the coupling reactions of 2-methyl-1H-
imidazole, 2-ethyl-1H-imidazole or 1H-benzo[d]imidazole with
phenylboronic acid were also performed well, and the
corresponding desired products were isolated in good yields
4
4
. Experimental
.1. General
The 3,2’-pypzpy, 4,2’-pypzpy, 2,3’-pypzpy and 2,4’-pypzpy
1
1b
(entries 10-12). Encouraged by the high efficiency for the
ligands were synthesized according to the literature method.
reaction of imidazole derivatives described above, we also
examined 1H-pyrazole, aniline and benzamide. As shown in
Table 2, the coupling reaction of 1H-pyrazole and phenylboronic
acid was performed well, and the desired product was isolated in
an excellent yield (entry 13). Reaction of aniline with 7a gave
diphenylamine in 55% yield (entry 14), while that of benzamide
with 7a gave the expected coupling product only in 15% yield
All other commercial reagents were used without further
purification. Column chromatography was performed on silica
gel. Electrospray ion mass spectra (ESI-MS) were performed on
an Agilent 1200/6200 mass spectrometer. High-resolution mass
spectra were obtained by using a Microma GCT-TOF instrument.
1
13
H NMR and C NMR spectra were recorded on recorded at
ambient temperature on a Varian UNITY plus-400 spectrometer.
1
(entry 15).
H chemical shifts were referenced to Me
residual protons in CDCl (δ 7.26 ppm), DMSO-d (δ 2.50 ppm).
13
4
Si (δ 0.0 ppm) and
1e,9b
3
6
The catalytic reaction mechanism
for the above cross-
C NMR spectra were reported relative to CDCl (δ 77.16 ppm),
3
coupling reactions is proposed as follows (Scheme 2). Firstly,
DMSO-d (δ 39.5 ppm). The uncorrected melting points were
6
reaction of complex 1 with O and H O may lead to the formation
2
2
determined on a Mel-Temo II apparatus.
of a hydroxo copper(II) intermediate A. Secondly, phenylboronic
acid may undergo transmetalation with the intermediate A to give
boric acid and the intermediate B. Thirdly, reaction of the
intermediate B with imidazole may give the intermediate C,
which might be oxidized into a Cu(III) intermediate D by O2.
Finally, the intermediate D may undergo reductive elimination to
yield complex 1 and the product, thus furnishing the catalytic
cycle.
4.2. Synthesis of [3,2'-pypzpym]I.
To a 100 mL round-bottomed flask fitted with reflux
condenser
yl)pyridine (2.22 g, 10 mmol), MeI (5.68 g, 40 mmol) and THF
20 mL). The mixture was refluxed for 6 h under N atmosphere.
was
added
2-(3-(pyridin-3-yl)-1H-pyrazol-1-
(
2
During this time, a yellow solid was precipitated in the flask. The
suspension was cooled to room temperature, and the supernatant
was decanted off. The resulting solid was washed with anhydrous
N
N
N
Et O for three times to afford the yellow solid of [3,2'-pypzpym]I.
2
Yield: 3.3 g, 92%. m.p. 405-406 ºC. Anal. Calcd for C H N I:
1
4
13
4
N
N
I
I
C, 46.17; H, 3.60; N, 15.38 %; Found: C, 46.02; H, 3.95; N,
CuI
N
CuIII
1
1
5.69 %. H NMR (400 MHz, DMSO-d , ppm): δ 9.65 (s, 1H),
6
2
H O
N
N
9.09-9.02 (m, 2H), 8.85 (d, J = 4.0 Hz, 1H), 8.56 (d, J = 4.0 Hz,
1H), 8.26 (t, J = 4.0 Hz, 1H), 8.13 (d, J = 4.0 Hz, 2H), 7.50-8.46
(D)
1
2 2
/2 O + H O
O
2
13
(
m, 1H), 7.40 (d, J = 4.0 Hz, 1H), 4.50 (s, 3H). C NMR (100
NH
H
MHz, DMSO-d , ppm): δ 150.6, 149.0, 147.3, 144.9, 142.9,
6
N
N
O
N
4+
N
N
140.8, 140.2, 132.3, 130.2, 128.5, 123.3, 113.0, 107.6, 48.8.
CuII
CuII
CuII
+
HRMS (EI) Calcd for C H N 237.1140, found 237.1142. IR
14
13
4
O
H
A)
N
N
−1
(KBr pellet, ν/cm ): 1636 (w), 1616 (w), 1594 (m), 1579 (m),
505 (w), 1471 (w), 1458 (s), 1444 (m), 1371 (m), 1325 (w),
(
C)
(
1
H
1296 (w), 1282 (m), 1205 (w), 1179 (w), 1146 (w), 1124 (w),
1065 (m), 992 (w), 958 (w), 825 (w), 797 (s), 785 (s), 717 (w),
676 (m), 621 (m), 511 (w).
N
B(OH)
2
N
CuII
B(OH)
3
N
N
(B)
4
.3. Synthesis of [4,2'-pypzpym]I.
Scheme 2. Proposed catalytic mechanism.
Yellow solid of [4,2'-pypzpym]I was obtained by the similar
approach to that used for the isolation of [3,2'-pypzpym]I, using
-(3-(pyridin-4-yl)-1H-pyrazol-1-yl)pyridine and MeI as starting
materials. Yield: 85 %. m.p. > 430 ºC. Anal. Calcd for C H N I:
2
3
. Conclusions
In summary, the assemblies of copper(I) iodide with four
1
4
13
4
C, 46.17; H, 3.60; N, 15.38 %; Found: C, 46.36; H, 3.78; N,
1
1
5.87 %. H NMR (400 MHz, DMSO-d , ppm): δ 9.04 (d, J = 8.0
pypzpymI ligands give rise to five anionic-[Cu I ]-based
6
x y
Hz, 2H), 8.90 (s, 1H), 8.63-8.57 (m, 3H), 8.16-8.11 (m, 2H), 7.58
coordination complexes 1-5. The structures of 1-4 are structurally
confirmed. In 2, 3,2'-pypzpym ligand is only used as counter ion.
The 3,2'-pypzpym, 4,2'-pypzpym and 2,3'-pypzpym anions in 1, 3
13
(
s, 1H), 7.51(t, J = 4.0 Hz, 1H), 4.34 (s, 3H); C NMR (100
MHz, DMSO-d , ppm): δ 150.6, 149.0, 148.1, 146.9, 146.4,
6
1
40.4, 130.7, 123.8, 123.2, 113.1, 109.3, 47.8. HRMS (EI) Calcd
6

+
−1
for C H N 237.1140, found 237.1142. IR (KBr pellet, ν/cm ):
1
(
1
7
0.05 mmol) and CuI (9.6 mg, 0.05 mmol) as starting materials in
14
13
4
ACCEPTED MANUSCRIPT
638 (s), 1593 (m), 1575 (w), 1546 (w), 1507 (w), 1469 (s), 1451
s), 1375 (s), 1326 (w), 1275 (m), 1241 (w), 1218 (m), 1190 (m),
120 (w), 1058 (w), 992 (w), 962 (w), 948 (w), 850 (w), 781 (m),
18 (w), 508 (w).
MeCN. Yield: 14.2 mg (76% based on Cu). Anal. Calcd (%) for
C H Cu I N : C, 22.57; H, 1.76; N, 7.52 %. Found: C, 22.46; H,
2
8
26
4 6
8
−1
1.81; N, 7.54 %. IR (KBr pellet, ν/cm ): 1630 (s), 1599 (w),
1570 (w), 1503 (w), 1477 (s), 1448 (s), 1371 (s), 1320 (s), 1277
(
w), 1190 (m), 1167 (w), 1066 (w), 963 (w), 845 (w), 787 (m)
4
.4. Synthesis of [2,3'-pypzpym]I.
,
775 (m), 716 (w).
Yellow solid of [2,3'-pypzpym]I was obtained by the similar
4
.8. Synthesis of [CuI (2,3'-pypzpym)] (4).
2
method to that used for the isolation of [3,2'-pypzpym]I, using 2-
1-(pyridin-3-yl)-1H-pyrazol-3-yl)pyridine and MeI as starting
materials. Yield: 89 %. m.p. > 430 ºC. Anal. Calcd for C H N I:
(
Compound 4 was prepared as orange crystals in a similar way
to that described for 1, using [2,3'-pypzpym]I (18.2 mg, 0.05
mmol) and CuI (9.6 mg, 0.05 mmol) as starting materials in
MeCN. Yield: 16.1 mg (58% based on Cu). Anal. Calcd (%) for
C H CuI N : C, 30.32; H, 2.36; N, 10.10 %. Found: C, 30.47;
H, 2.36; N, 10.28 %. IR (KBr pellet, ν/cm ): 1629 (m), 1586
(m), 1531 (m), 1511 (s), 1478 (w), 1459 (m), 1396 (m), 1370 (s),
1296 (m), 1241 (w), 1181 (w), 1156 (w), 1098 (w), 1059 (m),
970 (m), 818 (w), 797 (w), 770 (m), 713 (w).
14
13
4
C, 46.17; H, 3.60; N, 15.38 %; Found: C, 45.94; H, 3.83; N,
1
1
9
5.44 %. H NMR (400 MHz, DMSO-d , ppm): δ 9.78 (s, 1H),
6
.13 (d, J = 8.0 Hz, 1H), 9.00 (d, J = 8.0 Hz, 1H), 8.90 (d, J = 4.0
14
13
2
4
−1
Hz, 1H), 8.73 (d, J = 4.0 Hz, 1H), 8.35 (t, J = 4.0 Hz, 1H), 8.22(d,
J = 4.0 Hz, 1H), 8.01 (t, J = 8.0 Hz, 1H), 7.50 (d, J = 4.0 Hz, 1H),
13
7
.34 (d, J = 4.0 Hz, 1H), 4.53 (s, 3H); C NMR (400 MHz,
DMSO-d , ppm): δ 154.6, 150.0, 149.6, 142.5, 138.2, 137.1,
6
1
36.2, 132.7, 131.1, 128.2, 123.9, 120.3, 108.3, 48.5. HRMS (EI)
+
4.9. Synthesis of [(CuI )(2,4'-pypzpym)] (5).
2
Calcd for C H N 237.1140, found 237.1148. IR (KBr pellet,
14
13
4
−1
ν/cm ): 1591(s), 1539 (s), 1484 (m), 1457 (m), 1382 (s), 1371
m), 1281 (m), 1171 (m), 1094 (w), 963 (w), 812 (w), 778 (m),
Compound 5 was prepared as orange crystals in a similar
manner to that described for 1, using [2,4'-pypzpym]I (18.2 mg,
(
7
47 (w), 687 (w), 664 (w).
0
.05 mmol) and CuI (9.6 mg, 0.05 mmol) as starting materials in
MeCN. Yield: 23.5 mg (81% based on Cu). Anal. Calcd (%) for
C H CuI N : C, 30.32; H, 2.36; N, 10.10 %. Found: C, 30.89;
H, 2.59; N, 10.44 %. IR (KBr pellet, ν/cm ): 1637 (s), 1618 (s),
1538 (m), 1525 (w), 1410 (m), 1384 (m), 1375 (w), 1191 (m),
1138 (w), 1047 (w), 950 (w), 843 (w), 754 (w).
4
.5. Synthesis of [2,4'-pypzpym]I.
14
13
2
4
−1
Yellow solid of [2,3'-pypzpym]I was obtained by the similar
route to that used for the isolation of [3,2'-pypzpym]I, using 2-(1-
pyridin-4-yl)-1H-pyrazol-3-yl)pyridine and MeI as starting
(
materials. Yield: 94 %. m.p. 400-402 ºC. Anal. Calcd for
C H N I: C, 46.17; H, 3.60; N, 15.38 %; Found: C, 46.59; H,
4
.10. General catalytic procedure for the N-arylation of 1H-
14
13
4
1
imidazole with arylboronic acids.
3
.86; N, 15.13 %. H NMR (400 MHz, DMSO-d , ppm): δ 9.09
6
(
2
8
t, J = 8.0 Hz, 3H), 8.75 (d, J = 4.0 Hz, 1H), 8.61 (d, J = 8.0 Hz,
To a solution of 1 (0.02 mmol) in H O/MeCN (V/V = 2/1, 4
mL) was added 1H-imidazole (1.0 mmol) and arylboronic acid (2
2
H), 8.24 (d, J = 8.0 Hz, 1H), 8.02 (t, J = 8.0 Hz, 1H), 7.53 (t, J =
13
.0 Hz, 1H), 7.42 (d, J = 4.0 Hz, 1H), 4.34 (s, 3H). C NMR
mmol) under O atmosphere. The mixture was stirred at 60 ºC for
2
(100 MHz, DMSO-d , ppm): δ 156.4, 149.7, 149.5, 149.4, 147.0,
6
24 h. After cooling to ambient temperature, the mixture was
partitioned between water and CH Cl . The organic layer was
1
37.3, 132.3, 124.4, 120.6, 114.5, 110.1, 46.8. HRMS (EI) Calcd
+ −1
2
2
for C H N 237.1140, found 237.1146. IR (KBr pellet, ν/cm ):
1
14
13
4
separated, and the aqueous layer was extracted with CH Cl . The
2 2
683(s), 1591(w), 1544 (s), 1525 (s), 1482 (m), 1425 (w), 1372
combined organic layers were washed with brine, dried over
(s), 1316 (w), 1288 (w), 1213 (w), 1191 (m), 1148 (w), 1045 (m),
Na SO , and concentrated in vacuo. The residue was purified by
2
4
9
91 (w), 952 (m), 935 (m), 801 (w), 742 (w), 721 (w)
.6. Synthesis of [CuI (3,2'-pypzpym)] (1) and [(Cu I )(3,2'-
flash chromatography on silica gel.
9b 1
4
2
4
6
1-phenyl-1H-imidazole (8a). H NMR (400 MHz, DMSO-d6,
ppm): δ 8.16 (s, 1H), 7.62 (s, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.38
pypzpym) ] (2).
2
n
1
3
(
t, J = 8.0 Hz, 2H), 7.22 (t, J = 8.0 Hz, 1H), 7.02 (s, 1H).
C
To a MeCN (3 mL) solution of [3,2'-pypzpym]I (18.2 mg, 0.05
mmol) was added a solution of CuI (9.6 mg, 0.05 mmol) in
MeCN (3 mL). The mixture was stirred at room temperature for 2
NMR (100 MHz, DMSO-d , ppm): δ 137.3, 135.9, 130.3, 130.2,
6
+
1
1
27.2, 120.7, 118.4. HRMS m/z calcd for C H N [M + H]
9
9
2
45.0766, found 145.0763.
h and then filtered. The filtrate was layered with Et O (30 ml) to
2
9b
1
produce dark red crystals of 1 and yellow crystals of 2 in several
days. They were separated mechanically under microscope.
Complex 1: Yield: 6.4 mg (23 % based on Cu). Anal. Calcd for
C H CuI N : C, 30.32; H, 2.36; N, 10.10 %; Found: C, 30.57;
1-(4-methoxyphenyl)-1H-imidazole (8b).
H
NMR (400
MHz, DMSO-d , ppm): δ 8.15 (s, 1H), 7.65 (s, 1H), 7.57 (d, J =
6
1
3
8.0 Hz, 2H), 7.08 (d, J = 8.0 Hz, 3H), 3.81 (s, 3H). C NMR
14
13
2
4
(100 MHz, DMSO-d , ppm): δ 158.3, 135.8, 130.5, 129.9, 122.4,
6
−1
+
H, 2.47; N, 10.77 %. IR (KBr pellet, ν/cm ): 1630 (w), 1598(m),
509 (m), 1474 (s), 1438 (s), 1373 (s), 1317 (s), 1297 (w), 1183
118.7, 115.2, 55.8. HRMS m/z calcd for C H N O [M + H]
10
11
2
1
175.0871, found 175.0870.
(
(
w), 1159 (w), 1064 (w), 952 (w), 825 (w), 778 (m), 718 (w), 692
w).
9b 1
1
-(p-tolyl)-1H-imidazole (8c). H NMR (400 MHz, DMSO-
d , ppm): δ 8.20 (s, 1H), 7.69 (s, 1H), 7.52 (d, J = 8.0 Hz, 2H),
6
1
3
Complex 2: Yield: 6.5 mg (35 % based on Cu). Anal. Calcd
7.30 (d, J = 8.0 Hz, 2H), 7.09 (s, 1H), 2.33 (s, 3H). C NMR
for C H Cu I N : C, 22.57; H, 1.76; N, 7.52 %; Found: C,
2
1
(100 MHz, DMSO-d , ppm): δ 136.6, 135.8, 135.0, 130.6, 130.1,
2
8
26
4 6
8
6
−1
+
2.72; H, 2.04; N, 8.26 %. IR (KBr pellet, ν/cm ): 1635 (w),
120.6, 118.4, 20.84. HRMS m/z calcd for C H N [M + H]
10
11
2
594 (m), 1575 (m), 1504 (w), 1478 (s), 1455 (s), 1440 (s), 1370
159.0922, found 159.0919.
(s), 1325 (w), 1271 (m), 1208 (w), 1174 (w), 1121 (w), 1054 (m),
13 1
1
-(m-tolyl)-1H-imidazole (8d). H NMR (400 MHz, DMSO-
1
038 (w), 957 (w), 777 (m), 717 (m), 669 (w).
d , ppm): δ 8.23 (s, 1H), 7.72 (s, 1H), 7.48 (s, 1H), 7.44-7.36 (m,
6
1
3
4
.7. Synthesis of [Cu I (4,2'-pypzpym) ] (3).
2H), 7.16 (d, J = 8.0 Hz, 1H), 7.10 (s, 1H), 2.37 (s, 3H).
C
4
6
2
NMR (100 MHz, DMSO-d , ppm): δ 139.9, 137.2, 135.8, 130.2,
6
Compound 3 was prepared as orange crystals in a similar
manner to that described for 1, using [4,2'-pypzpym]I (18.2 mg,
7

1
30.0, 128.0, 121.2, 118.3, 117.8, 21.35. HRMS m/z calcd for
143.4, 129.3, 119.6, 116.8. HRMS m/z calcd for C H N [M +
H] 170.0970, found 170.0972.
ACCEPTED MANUSCRIPT
12 12
+
+
C H N [M + H] 159.0922, found 159.0924.
10
11
2
9b
1
18
1
1
-(o-tolyl)-1H-imidazole (8e). H NMR (400 MHz, DMSO-
N-Phenylbenzamide (8o).
H NMR (400 Hz, DMSO-d6,
d , ppm): δ 7.82 (s, 1H), 7.40 (t, J = 8.0 Hz, 3H), 7.36-7.28 (m,
ppm): δ 10.27 (s, 1H), 7.98 (d, J = 7.3 Hz, 2H), 7.81 (d, J = 7.9
Hz, 2H), 7.62 – 7.56 (m, 1H), 7.53 (t, J = 7.3 Hz, 2H), 7.36 (t, J =
7.8 Hz, 2H), 7.11 (t, J = 7.3 Hz, 1H). C NMR (100 MHz,
6
13
2
H), 7.09 (s, 1H), 2.15 (s, 3H). C NMR (100 MHz, DMSO-d6,
13
ppm): δ 137.6, 136.5, 133.1, 131.1, 128.6, 128.4, 126.9, 126.2,
+
1
20.8, 17.3. HRMS m/z calcd for C H N [M + H] 159.0922,
DMSO-d , ppm): δ 165.6, 139.2, 135.0, 128.7, 128.5, 128.2,
10
11
2
6
+
found 159.0925.
127.7, 127.6, 120.2. HRMS m/z calcd for C H NO [M + H]
13
12
6d
1
198.0919, found 198.0916.
1
-(4-(trifluoromethyl)phenyl)-1H-imidazole (8f).
H NMR
(
7
1
400 MHz, DMSO-d , ppm): δ 8.47 (s, 1H), 7.96-7,90 (m, 5H),
4.11. A X-ray crystallography.
6
13
.21 (s, 1H). C NMR (100 MHz, DMSO-d , ppm): δ 140.3,
6
Single crystals of 1-4 were obtained directly from the above
preparations. X-ray diffraction data collection was performed on
a Xcalibur, Atlas, Gemini (1 and 2) or a Bruker APEX-II CCD (3
and 4) X-ray diffractometer by using graphite monochromated
30.9, 127.4, 127.2, 125.3, 123.5, 121.7, 120.9. HRMS m/z calcd
+
for C H F N [M + H] 213.0640, found 213.0636.
10
8
3
2
14 1
1
-(4-nitrophenyl)-1H-imidazole (8g).
H NMR (400 MHz,
DMSO-d , ppm): δ 8.51 (s, 1H), 8.36 (d, J = 8.0 Hz, 2H), 7.98 (d,
Mo K (λ = 0.71073 Å). Single crystals of 1-4 were mounted with
6
α
13
J = 12.0 Hz, 3H), 7.19 (s, 1H). C NMR (100 MHz, DMSO-d6,
ppm): δ 145.7, 142.1, 136.5, 131.3, 125.9, 120.8, 118.3. HRMS
grease at the top of a glass fiber. 1, 2 and 3 were cooled to 223 K
in a liquid-nitrogen stream while 4 was kept at 153 K. The
collected data were reduced by using the program Bruker APEX2
or CrysAlisPro, Agilent Technologies (CrysAlis171 .NET,
Version 1.171.36.28) and an absorption correction (multi-scan)
was applied. The reflection data were also corrected for Lorentz
and polarization effects. The reflection data were also corrected
for Lorentz and polarization effects. The structures of 1-4 were
solved by direct method applying SHELXS-97 program and
+
m/z calcd for C H N O [M + H] 190.0617, found 190.0618.
9
8
3
2
14
1
1
-([1,1'-biphenyl]-4-yl)-1H-imidazole (8h).
H NMR (400
MHz, DMSO-d , ppm): δ 8.33 (s, 1H), 7.80 (d, J = 4.0 Hz, 3H),
6
7
1
.76-7.70 (m, 4H), 7.48 (t, J = 8.0 Hz, 2H), 7.38 (t, J = 8.0 Hz,
13
H), 7.14 (s, 1H). C NMR (100 MHz, DMSO-d , ppm): δ
6
1
1
39.4, 138.9, 136.6, 135.9, 130.4, 129.4, 128.4, 128.1, 126.9,
+
21.1, 118.3. HRMS m/z calcd for C H N [M + H] 221.1079,
2 19
15
13
2
refined by full matrix least-squares on F . All the non-H atoms
found 221.1080.
2
were refined on F anisotropically by full-matrix least squares
15 1
1
-(naphthalen-2-yl)-1H-imidazole (8i). H NMR (400 MHz,
method. All hydrogen atoms were introduced at the calculated
positions and included in the structure-factor calculations. A
summary of the important crystallographic information for 1-4
are summarized in Table S1. The selected bond distances and
angles of 1-4 are listed in Table S2.
DMSO-d , ppm): δ 8.41 (s, 1H), 8.20 (s, 1H), 8.08 (d, J = 8.0 Hz,
6
1
H), 7.97 (t, J = 8.0 Hz, 2H), 7.87 (t, J = 12.0 Hz, 2H), 7.61-7.52
13
(m, 2H), 7.17 (s, 1H). C NMR (100 MHz, DMSO-d , ppm): δ
6
1
1
36.2, 134.8, 133.7, 131.8, 130.4, 130.2, 128.2, 128.1, 127.6,
26.5, 120.0, 118.5, 117.8. HRMS m/z calcd for C H N [M +
13
11
2
+
H] 195.0922, found 195.0924.
Acknowledgments
15 1
2
-methyl-1-phenyl-1H-imidazole (8j). H NMR (400 MHz,
This work was financially supported by the National Natural
Science Foundation of China (Grant Nos. 21373142 and
CDCl ): δ 7.38 (d, J = 6.5 Hz, 2H), 7.33 (d, J = 6.0 Hz, 1H), 7.19
3
13
(d, J = 7.5 Hz, 2H), 6.92 (d, J = 11.1 Hz, 2H), 2.27 (s, 3H). C
2
1471108 and 21531006), the Natural Science Foundation of
NMR (151 MHz, CDCl ): δ 144.6, 138.0, 129.4, 128.1, 127.6,
3
Jiangsu Province (BK20161276), the State Key Laboratory of
Organometallic Chemistry of Shanghai Institute of Organic
Chemistry (2015kf-07), the “333” Project of Jiangsu Province,
the Priority Academic Program Development of Jiangsu Higher
Education Institutions, the “SooChow Scholar” Program of
Soochow University. The authors are grateful to the useful
comments of the reviewers and the editor.
+
1
1
25.5, 120.6, 13.7. HRMS m/z calcd for C H N [M + H]
10 11 2
59.0922, found 159.0921.
16 1
2
-ethyl-1-phenyl-1H-imidazole (8k).
H NMR (400 MHz,
CDCl ): δ 7.48 (t, J = 7.2 Hz, 2H), 7.45-7.39 (m, 1H), 7.29 (d, J
3
=
7.4 Hz, 2H), 7.02 (d, J = 31.3 Hz, 2H), 2.67 (q, J = 7.5 Hz,
13
2
1
H), 1.25 (t, J = 7.5 Hz, 3H). C NMR (151 MHz, CDCl ): δ
49.6, 138.0, 129.5, 128.3, 127.6, 125.9, 120.7, 20.6, 12.4.
3
+
HRMS m/z calcd for C H N [M + H] 173.1079, found
Supplementary data
11
13
2
1
73.1081.
9
b
1
Crystal data and refinement parameters for 1-4 (CCDC No.
485367-1485370). The H and C NMR spectra for the isolated
products for this article can be found in online version at doi:
1
-phenyl-1H-benzo[d]imidazole (8l). H NMR (400 MHz,
1
13
1
DMSO-d ): δ 8.56 (s, 1H), 7.81-7.76 (m, 1H), 7.68 (d, J = 7.7
Hz, 2H), 7.65-7.60 (m, 3H), 7.50 (t, J = 7.2 Hz, 1H), 7.32 (p, J =
.9 Hz, 2H). C NMR (151 MHz, DMSO-d ): δ 143.8, 143.3,
35.0, 133.1, 130.1, 127.7, 123.7, 123.5, 122.4, 119.9, 110.6.
6
13
7
1
6
References and notes
+
HRMS m/z calcd for C H N [M + H] 195.0922, found
13
11
2
1
(a) Monnier, F.; Taillefer, M. Angew. Chem. Int. Ed. 2009, 48, 6954-
971; (b) Wolfe, J. P.; Wagaw, S.; Marcoux, J. F.; Buchwald, S. L. Acc.
1
95.0924.
6
17 1
Chem. Res. 1998, 31, 805-818; (c) Shen, Q. L.; Hartwig, J. F.J. Am.
Chem. Soc. 2007, 129, 7734-7735; (d) Xie, Y. X.; Pi, S. F.; Wang, J.;
Yin, D. L.; Li, J. H. J. Org. Chem. 2006, 71, 8324-8327; (e) Onaka, T.;
Umemoto, H.; Miki, Y.; Nakamura, A.; Maegawa, T.; J. Org. Chem.
2014, 79, 6703−6707; (f) Zhou, Y. P.; Xie, Y. J.; Yang, L.; Xie, P.;
Huang, H. M. Tetrahedron Lett. 2013, 54, 2713-2716.
1
-Phenyl-1H-pyrazole (8m). H NMR (400 MHz, DMSO-d6)
δ 8.50 (s, 1H), 7.84 (d, J = 7.6 Hz, 2H), 7.75 (s, 1H), 7.49 (t, J =
.3 Hz, 2H), 7.30 (t, J = 7.0 Hz, 1H), 6.54 (s, 1H). C NMR (101
MHz, DMSO-d ) δ 140.7, 139.7, 129.2, 127.7, 126.3, 118.2,
13
7
6
+
1
1
07.7. HRMS m/z calcd for C H N [M + H] 145.0766, found
9 9 2
45.0763.
2
(a) Ullman, F. Ber. Dtsch. Chem. Ges. 1903, 36, 2389-2391; (b)
Goldberg, I. Ber. Dtsch. Chem. Ges. 1906, 39, 1691-1692; (c) Li, F. W.;
Andy Hor, T. S. Chem. Eur. J. 2009, 15, 10585-10592.
18 1
Diphenylamine (8n). H NMR (400 MHz, CDCl , ppm): δ
.14 (s, 1H), 7.22 (t, J = 7.7 Hz, 4H), 7.07 (d, J = 7.9 Hz, 4H),
.81 (t, J = 7.2 Hz, 2H). C NMR (100 MHz, CDCl , ppm): δ
3
8
6
13
3
8

3
4
(a) Hartwig, J. F.Angew. Chem. Int. Ed. Engl. 1998, 37, 2046-2067; (b)
ACCEPTED MANUSCRIPT
Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125-146.
c) Shakespeare, W. C. Tetrahedron Lett. 1999, 40, 2035-2038.
(
(a) Chan, D. M. T.; Monaco, K. L.; Wang, R. P.; Winters, M. P.
Tetrahedron Lett. 1998, 39, 2933-2936; (b) Lam, P. Y. S.; Clarkt, C. G.;
Saubernt, S.; Adamst, J.; Winters, M. P.; Chan, D. M. T.; Combs, A.
Tetrahedron Lett. 1998, 39, 2941-2944.
5
6
(a) Rao, K. S.; Wu, T. S. Tetrahedron 2012, 68, 7735-7754; (b) Chiang,
G. C. H.; Olsson, T. Org. Lett. 2004, 6, 3079-3082; (c) Zhang, Z. H.;
Yu, Y.; Liebeskind, L. S. Org. Lett. 2008, 10, 3005-3008; (d) Liu, B.;
Liu, B.; Zhou, Y. B.; Chen, W. Z. Organometallics 2010, 29, 1457-
1
464.
(a) Debreczeni, N.; Fodor, A.; Hell, Z. Catal. Lett. 2014, 144, 1547-
1
551; (b) Roy, S.; MSarma, . J.; Kashyap, B.; Phukan, P. Chem.
Commun. 2016, 52, 1170-1173; (c) Zhang, L. Y.; Wang, L. Chin. J.
Chem. 2006, 24, 1605-1608; (d) Kantam, M. L.; Venkanna, G. T.;
Sridhar, C.; Sreedhar, B.; Choudary, B. M. J. Org. Chem. 2006, 71,
9
522-9524.
7
8
Kantam, M. L.; Neelima, B.; Reddy, C. V.; Neeraja, V. J. Mol. Cat. A:
Chem. 2006, 249, 201-206.
(a) Gallon, B. J.; Kojima, R. W.; Kaner, P. L.; Diaconescu, P. L. Angew.
Chem. Int. Ed. 2007, 46, 7251-7254; (b) Liu, C.; Zhang, Y. X.; Liu, N.;
Qiu, J. S. Green Chem. 2012, 2999-3003; (c) Bakherad, M.; Jajarmi, S.
J. Mol. Catal. A: Chem. 2013, 370, 152-159; (d) Amadio, E.; Scrivanti,
A.; Beghetto, V.; Bertoldini, M.; Mahbubul Alam, M.; Matteoli, U. RSC
Advances 2013, 3, 21636-21640.
9
(a) Lan, J. B.; Chen, L.; Yu, X. Q.; You, J. S.; Xie, R. G. Chem.
Commun. 2004, 188-189; (b) Collman, J. P.; Zhong, M.; Zeng, L.;
Costanzo, S. J. Org. Chem. 2001, 66, 1528-1531; (c) Joubert, N.; Baslé,
E.; Vaultier, M.; Pucheault, M. Tetrahedron Lett. 2010, 51, 2994-2997;
(d) Yue, Y.; Zheng, Z. G.; Wu, B.; Xia, C. Q.; Yu, X. Q. Eur. J. Org.
Chem. 2005, 5154-5157. (e) Sreedhar, B.; Venkanna, G. T.; Kumar, K.
B. S.; Balasubrahmanyam, V. Synthesis 2008, 795-799.
1
1
0
1
(a) Tan, D. W.; Xie, J. B.; Li, Q.; Li, H. X.; Li, J. C.; Li, H. Y.; Lang, J.
P. Dalton Trans. 2014, 43, 14061-14071; (b) Li, Q.; Zhang, L. M.; Bao,
J. J.; Li, H. X.; Xie, J. B.; Lang, J. P. Appl. Organometal. Chem. 2014,
2
8, 861-867; (c) Wan, L. M.; Li, H. X.; Zhao, W.; Ding, H. Y.; Fang, Y.
Y.; Ni, P. H.; Lang, J. P. J. Poly. Sci. Part. A 2012, 50, 4864–4870.
(a) Xu, Z. L.; Li, H. X.; Ren, Z. G.; Du, W. Y.; Xu, W. C.; Lang, J. P.
Tetrahedron 2011, 67, 5282-5288; (b) Shi, J.; Li, F. L.; Li, H. X.; Wang,
F.; Yu, H.; Ren, Z. G.; Zhang, W. H.; Lang, J. P. Inorg. Chem. Commun.
2
014, 46, 159-162; (c) Tan, D. W.; Li, H. X.; Young, D. J.; Lang, J. P.
Tetrahedron 2016, 72, 4169-4176.
1
1
2
3
Li, J. C.; Li, H. X.; Li, H. Y.; Gong, W. J.; Lang, J. P. Cryst. Growth
Des. 2016, 16, 1617-1625.
Liu, L. B; Frohn, M.; Xi, N.; Dominguez, C.; Hungate, R.; Reider, P. J.
J. Org. Chem. 2005, 70, 10135-10138.
1
1
1
4
5
6
Ma, H. C.; Jiang, X. Z. J. Org. Chem. 2007, 72, 8943-8946.
Suresh, P.; Pitchumani, K. J. Org. Chem. 2008, 73, 9121-9124.
Shi, S. Y.; Zhang, Y. H.; Zhao, J. L. China Invention Patent
CN101260081A, 2008.
1
1
1
7
8
9
Sperotto, E.; Klink, G. P. M. v.; Vries, J. G. D., Koten, G. V.
Tetrahedron 2010, 66, 3478-3484.
Raghuvanshi, D. S.; Gupta, A. K.; Singh, K. N. Org. Lett. 2012, 14,
4
326-4329.
Sheldrick, G. M. Acta Cryst. 2015, C71, 3-8.
Received: ((will be filled in by the editorial staff))
Published online: ((will be filled in by the editorial staff))
9