A Chemoselective and Desulfurative Chan–Lam Coupling: C–N Bond Formation between Benzimidazoline-2-Thiones and Arylboronic Acids

Article abstract of DOI:10.1002/ejoc.202000075

An efficient method for the chemoselective and desulfurative Chan–Lam cross-coupling based on benzimidazoline-2-thiones was developed. By modulating the amount of the catalyst Cu(OAc)₂·H₂O, alkali, temperature, and solvent, the desulfurizational C–N bond formation product (N-arylbenzimidazoles) could be selectively furnished smoothly. The features of this protocol are an inexpensive and readily available catalyst, ligand-free conditions, wide substrate scope, easy performance, and moderate to excellent yields. It shows potential synthetic value for the preparation of a diversity of arylbenzoheterocyclic compounds, which are potentially active in pharmaceuticals and agrochemicals.

Full text of DOI:10.1002/ejoc.202000075

A Journal of
Accepted Article
Title: A Chemoselective and Desulfurative Chan-Lam Coupling: C-
N Bond Formation between Benzimidazoline-2-Thiones and
Arylboronic Acids
Authors: Jin-Quan Chen, Xing Liu, Jia Guo, and Zhi-Bing Dong
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10.1002/ejoc.202000075
European Journal of Organic Chemistry
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A Chemoselective and Desulfurative Chan-Lam Coupling: C-N
Bond Formation between Benzimidazoline-2-Thiones and
Arylboronic Acids
Jin-Quan Chen,[a] Xing Liu,[a] Jia Guo,[b],[c] and Zhi-Bing Dong* [a],[b],[c],[d]
Abstract: An efficient method for the chemoselective and
desulfurative Chan-Lam cross-coupling based on benzimidazoline-2-
thiones was developed. By modulating the amount of the catalyst
Cu(OAc)2•H2O, alkali, temperature and solvent, the desulfurizational
C-N bond formation product (N-arylbenzimidazoles) could be
selectively furnished smoothly. The features of this protocol are an
inexpensive and readily available catalyst, ligand-free conditions,
wide substrate scope, easy performance, and moderate to excellent
yields. It shows potential synthetic value for the preparation of a
diversity of arylbenzoheterocyclic compounds, which are potentially
active in pharmaceuticals and agrochemicals.
and copper-catalyzed couplings of N-H substrates with NaBPh4
(Scheme 1, e) are also optional pathways.[8] However, these
synthetic processes suffer from harsh reaction conditions such
as high reaction temperature, requirement of stoichiometric
amount of copper catalyst, or usage of toxic solvents and non-
commercially available ligands. Though N-arylations via cross-
coupling reactions between benzimidazoles and arylboronic
acids have been reported (Scheme 1, f),[9-10] the expanded
research based on classic Chan-Lam coupling is still desirable.
Introduction
Imidazole-based compounds are a class of very important and
versatile nitrogen-containing heterocyclic compounds due to
their numerous applications, such as drugs, pharmaceutical
intermediates, agrochemicals, antimicrobial agents, functional
materials, and biomimetic catalysts.[1] Among these, the N-
arylbenzimidazoles have attracted much attention since they are
key building blocks in a large number of pharmaceutical
molecules (Figure 1).[2] Besides, the N-arylbenzimidazoles also
have many comprehensive applications in other respects. For
instance, they can be applied in the synthesis of natural
products, and they are also fundamental materials for ionic
liquids, ligands for transition-metal catalysis, and versatile N-
heterocyclic carbene precursors.[3] Thus, the development of
simple and efficient approaches for the synthesis of N-
arylbenzimidazoles has attracted considerable attention in the
past decades.
Figure 1. Some biologically active N-arylbenzimidazoles.
Several strategies have been developed for the synthesis of N-
arylbenzimidazoles (Scheme 1). Synthetic protocols that afford
N-arylbenzimidazoles
catalyzed Ullmann-type
generally
involve
cross-couplings
transition-metal-
between
benzimidazoles and aryl halides (Scheme 1, a),[4] intramolecular
cross coupling of aromatic o-diamines with CO2 (Scheme 1, b),[5]
or cyclization of aromatic o-diamines with CO2 and H2 (Scheme
1, c).[6] In addition, N-arylation of azole compounds using
reactive and selective TMP-iodonium(III) salts (Scheme 1, d),[7]
[a]
[b]
[c]
[d]
School of Chemistry and Environmental Engineering, Wuhan
Institute of Technology, Wuhan 430205, China.
Scheme 1. Existing Synthetic Strategies towards N-arylbenzimidazoles.
Key Laboratory of Green Chemical Process, Ministry of Education,
Wuhan Institute of Technology, Wuhan 430205, China
Hubei Key Laboratory of Novel Reactor and Green Chemistry
Technology, Wuhan Institute of Technology, Wuhan 430205, China
Ministry-of-Education Key Laboratory for the Synthesis and
Application of Organic Functional Molecules, Hubei University,
Wuhan 430062, China.
Recently, we disclosed an efficient chemoselective Chan–Lam
coupling reactions between benzimidazoline-2-thiones and
arylboronic acids,[11] and the coupling reactions could be
selectively directed to two different products (Scheme 2, S-
arylbenzimidazoles or N,S-diarylbenzimidazoles). On the other
Email: dzb04982@wit.edu.cn
https://cee.wit.edu.cn/info/1052/1538.htm
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10.1002/ejoc.202000075
European Journal of Organic Chemistry
FULL PAPER
hand, it is known that desulfurative couplings, such as the
Liebeskind reaction[12] or the Suzuki-Miyaura reaction,[13] are
generally performed under harsh reaction conditions, which
usually involve the use of expensive transition metal catalysts
and ligands, high temperature, as well as the use of inert
atmosphere for the construction of C-C bonds.[14] As part of our
longstanding interest in heterocyclic chemistry[12] and
organosulfur chemistry in the development of Chan-Lam
catalyst (entry 13). In addition, the screenings also showed that
the yields obtained from Cu(II) salts were slightly higher than the
ones obtained from Cu(I) salts. The catalyst loading (entries 20-
22) indicated that 0.1 equiv. of Cu(OAc)2•H2O was optimal (entry
21). To further optimize the reaction conditions, we screened the
substrate ratio, the temperature, and the solvent (entry 23-33),
while the yield of 3a could not be improved. Thus, the optimal
reaction conditions for desired product 3a were as follows: 1a:2a
= 1:1.5, Cu(OAc)2•H2O (10 mol%), NaHCO3 (2.0 equiv), DMSO
(3 mL), 100 oC, 8h (entry 21).
couplings,[13] we herein disclose
a
chemoselective and
desulfurative Chan–Lam coupling which affords C-N formation
products (N-arylbenzimidazoles, Scheme 2) starting from
benzimidazoline-2-thiones and arylboronic acids. The selectivity
can be controlled by modulating the amount of Cu(OAc)2•H2O,
base, temperature and solvent, which could provides attractive
and alternative approach to access these important compounds.
Table 1. Optimization of Desulfurizational Chan–Lam Coupling for the
Synthesis of 3a.[a]
Catalyst
[Cu]
Yield
3a
Entry
Base
Ligand Solvent
(%)[b]
0
.
1
2
3
4
5
6
7
8
9
--
Cu(OAc)2 H2O(0.2eq.)
BPy[c]
BPy
BPy
BPy
BPy
BPy
BPy
BPy
BPy
BPy
BPy
BPy
--
--
--
--
--
--
--
--
--
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
.
KOH(2eq.)
NaOH(2eq.)
Cu(OAc)2 H2O(0.2eq.)
62
71
64
65
47
88
N.R.[d]
trace
58
80
N.R.
86
72
52
75
77
82
68
.
Cu(OAc)2 H2O(0.2eq.)
.
K2CO3(2eq.)
Na2CO3(2eq.)
Cs2CO3(2eq.)
NaHCO3(2eq.)
pyridine(2eq.)
EtN3(2eq.)
NaHCO3(1eq.)
NaHCO3(3eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
Cu(OAc)2 H2O(0.2eq.)
.
Cu(OAc)2 H2O(0.2eq.)
.
Cu(OAc)2 H2O(0.2eq.)
.
Cu(OAc)2 H2O(0.2eq.)
.
Cu(OAc)2 H2O(0.2eq.)
.
Cu(OAc)2 H2O(0.2eq.)
.
10
11
12
13
14
15
16
17
18
19
20
21
22
23[e]
24[f]
25[g]
26[h]
27[i]
28[j]
29
30
31
32
33
Cu(OAc)2 H2O(0.2eq.)
.
Cu(OAc)2 H2O(0.2eq.)
Scheme 2. Chan-Lam-type Coupling Reactions: (i) Previous Work:
Chemoselective C-S and C-N Bond Formations. (ii)This Work:
Desulfurizational C-N Coupling.
--
.
Cu(OAc)2 H2O(0.2eq.)
CuSO4(0.2eq.)
.
CuCl2 2H2O(0.2eq.)
CuBr2(0.2eq.)
CuI(0.2eq.)
CuCl(0.2eq.)
Results and Discussion
Cu(OTf)2(0.2eq.)
Thus, the reaction condition survey for the chemoselective and
desulfurative Chan–Lam coupling reaction of benzimidazoline-2-
thione (1a) with phenylboronic acid (2a) are summarized in
Table 1. Initially, the reaction of benzimidazoline-2-thione (1a)
and phenylboronic acid (2a) was examined in DMSO at 100 °C
in the presence of Cu(OAc)2•H2O (0.2 eq.) and 2,2'-bipyridine
(Bpy; 0.2 equiv). A mixture of S-arylbenzimidazole and N,S-
diarylbenzimidazole were detected simultaneously (entry 1)
without the addition of base. To our delight, the N-arylation
product 3a was obtained with 62% yield as the single product
when KOH (2.0 eq.) was added (entry 2), which demonstrated
that base was crucial to afford the desulfurative N-arylation
product. Encouraged by this result, various bases were
screened (entry 2-9), revealing that NaHCO3 was superior to
other bases, providing the desired product 3a in 88% yield (entry
7). Next, the amount of NaHCO3 was surveyed (entry 10-11),
and it was found that 2 equiv. of NaHCO3 was the optimal. The
control experiment for copper catalyst Cu(OAc)2•H2O and ligand
Bpy revealed that copper catalyst was crucial for the reaction
while ligand was not necessary (entry 12). Based on these
results, several copper catalysts were screened (entry 13-19)
and it showed that Cu(OAc)2•H2O was the most effective
.
NaHCO3(2eq.) Cu(OAc)2 H2O(0.05eq.)
82
92
79
79
.
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
NaHCO3(2eq.)
Cu(OAc)2 H2O(0.1eq.)
.
Cu(OAc)2 H2O(1.0eq.)
--
--
--
--
--
--
--
--
.
Cu(OAc)2 H2O(0.1eq.)
.
Cu(OAc)2 H2O(0.1eq.)
92
.
Cu(OAc)2 H2O(0.1eq.)
N.R.
N.R.
44
74
75
.
Cu(OAc)2 H2O(0.1eq.)
.
Cu(OAc)2 H2O(0.1eq.)
.
Cu(OAc)2 H2O(0.1eq.)
.
Cu(OAc)2 H2O(0.1eq.)
.
Cu(OAc)2 H2O(0.1eq.)
--
--
DMAc
H2O
65
.
Cu(OAc)2 H2O(0.1eq.)
N.R.
N.R.
N.R.
.
Cu(OAc)2 H2O(0.1eq.)
--
--
PhCH3
1,4-
.
Cu(OAc)2 H2O(0.1eq.)
dioxane
[a] Reaction conditions: 1a (0.5 mmol), 2a (0.75 mmol), base (2.0 equiv.),
solvent (3 mL), temperature : 100 oC, stirred for 6-8 h. [b] Isolated yield based
on 1a. [c] Bpy = 2,2'-bipyridine (0.2 equiv.). [d] No Reaction. [e] 1a : 2a = 1:1.
[f] 1a : 2a = 1:2. [g] temperature: 25 oC. [h] temperature: 60 oC. [i] temperature:
80 oC. [j] temperature: 120 oC.
With the optimal conditions established, we next explored the
scope of this desulfurative Chan–Lam coupling by employing
structurally diverse arylboronic acids and benzimidazoline-2-
thiones, and the results are summarized in Table 2. It was
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10.1002/ejoc.202000075
European Journal of Organic Chemistry
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satisfying that a serious of substituted phenylboronic acids could
couple with benzimidazoline-2-thione in moderate to excellent
yields. Phenylboronic acids bearing electron-withdrawing groups
(F, Cl, Br, CN) successfully coupled with benzimidazoline-2-
thione, providing the desired products (3b-3g, 3r) in moderate to
good yields (49%-79%), and electron-donating groups on the
phenylboronic acids gave the corresponding products (3h-3p)
with moderate to excellent yields (51%-98%). The investigation
results indicated that the electronic nature of the substituent
somehow effected the reaction. The electron donating
arylboronic acids were more reactive than the electron
withdrawing ones. The steric effect on this transformation was
also studied. Thus, disubstituted arylboronic acids (with ortho-,
meta- and para- groups) were employed, giving the
corresponding products N-arylbenzimidazoles (3i-3k) with 51%-
82% yields, which showed a certain steric effect. To our delight,
4-(methoxycabonyl)phenylboronic acid was also suitable for this
transformation, giving the intended product 3q in 70% yield.
Furthermore, 1-naphthylboronic acid and 2-naphthylboronic acid
successfully coupled with benzimidazoline-2-thione, giving the
target products 3s and 3t in good yields (62% and 71%),
respectively.
Subsquently, we continued to explore the substrate scope either
for benzimidazoline-2-thiones or for arylboronic acids, and the
results are listed in Table 3. It was gratifying to find that whether
the electron-donating or the electron-withdrawing groups
attaching to the substituted benzimidazoline-2-thiones reacted
with a variety of substituted arylboronic acids in moderate to
good yields, showing good substrate compatibility of this
protocol. The substrates surveyed also revealed that
benzimidazoline-2-thiones
bearing
electron-withdrawing
substituents were more reactive than the electron-donating ones
(3ze vs 3u, 3zf vs 3zb), and arylboronic acids bearing electron
donating groups showed higher yields than the ones with
electron withdrawing groups (3zb vs 3v, 3zf vs 3zh, 3zk vs 3zm).
Table 3. Substrate Scope for the Desulfurative Chan-Lam Reaction of
Substituted Arylboronic Acids with Benzimidazoline-2-thiones.[a]
Table 2. Substrate Scope for the Desulfurizational Chan-Lam Reaction of
Substituted Arylboronic Acids with Benzimidazoline-2-thione.[a]
[a]Reaction conditions: 1 (0.5 mmol), 2 (0.75 mmol), Cu(OAc)2•H2O (10 mol%),
NaHCO3 (2.0 equiv.), DMSO (3 mL), 100 oC, open air for 8-24 h; Isolated yield
based on 1.
To further explore the mechanism of this desulfurative C-N
coupling, the following control experiments were performed
(Scheme 3). Firstly, benzimidazoline-2-thione was treated with
NaHCO3 in DMSO at 100 oC for 20 h. In the reaction, the
starting material benzimidazoline-2-thione was remained a lot
and the desulfurative product benzimidazole was detected
(isolation yield: 30%). The yield of benzimidazole could not be
improved when the reaction time was prolonged to 48 h.
Sequently, arylboronic acid (1.5 equiv.) and Cu(OAc)2•H2O (10
mol%) were added to the hybrid system, and the mixture
[a]Reaction conditions: 1 (0.5 mmol), 2 (0.75 mmol), Cu(OAc)2•H2O (10 mol%),
NaHCO3 (2.0 equiv.), DMSO (3 mL), 100 oC, open air for 8-24 h; Isolated yield
based on 1.
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10.1002/ejoc.202000075
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(benzimidazoline-2-thione and benzimidazole) were transformed
to N-arylbenzimidazole smoothly (isolation yield: 92%), which
might be due to the driving force of Chan-Lam C-N coupling. To
further confirm the fact of this desulfurative Chan-Lam coupling,
diarylbenzimidazoles starting from benzimidazoline-2-thiones
and arylboronic acids, by modulating the amount of
Cu(OAc)2•H2O, base, temperature, and solvent. The protocol
features good selectivity, broad functional group tolerance, easy
product 3g was characterized by X-ray crystallography (Figure 2, performance and moderate to excellent yields. This protocol
CCDC 1953877), and it was identified with our speculated
reaction pathway.
showed potential application value for the preparation of a
diversity of N-aryl benzoheterocyclic compounds, which are
potentially active in pharmaceuticals and agrochemicals.
Experimental Section
Scheme 3. Control Experiments
Flash column chromatography was operated on silica gel with petroleum
ether-EtOAc (PE-EA) as the eluent. Thin layer Chromatography was
adopted and visualized under UV light. The RY-1G instrument was
adopted to determine melting points of target compounds. The HRMS
(high-resolution mass spectra) was recorded from a Finnigan MAT 95Q
mass instrument (ESI). A Bruker AM400 NMR instrument was operated
in CDCl3 to record NMR spectra.
Figure 2. X-ray Crystallography of Product 3g from the Desulfurizational
Chan-Lam Coupling.
According to the above experimental results and previous
literature reports,[17] we proposed a possible mechanism for this
reaction (Scheme 4). Firstly, the benzimidazoline-2-thione was
transformed to 2-mercaptobenzimidazole via isomerization (it is
a dynamic equilibrium), followed by desulfuration under the
action of base (NaHCO3), giving benzimidazole (a dynamic
equilibrium as well). Secondly, the arylboronic acid reacted with
the copper catalyst (A) to form complex B, which could be
oxidized by O2 to give Cu(III) species, and the subsequent
transmetalation with readily available desulfurative intermediate
(benzimidazole) gave intermediate C. Intermediate C easily
provided the desired C-N coupling product D along with Cu(I)
species (E) by reductive elimination. E was then oxidized by
oxygen to regenerate Cu(II) catalyst A.
Typical procedure for the synthesis of N-arylbenzimidazoles 3a (TP).
Benzimidazoline-2-thione 1a (0.5 mmol) and phenylboronic acid 2a (0.75
mmol), Cu(OAc)2•H2O (0.05 mmol), NaHCO3 (1.0 mmol) were added to a
dried tube (open to air) equipped with a magnetic stirring bar, DMSO (3.0
mL) was then added. The mixture was stirred at 100 oC and checked by
TLC. The reaction was quenched with sat. NH4Cl solution and then
extracted with ethyl acetate. The preliminary solution was dried over
Na2SO4 and evaporated. The crude material was further purified by
column chromatography to get the intended product 3a.
Analytical data of the products
Scheme 4. Proposed Reaction Mechanism.
1-phenyl-1H-benzo[d]imidazole (3a) [5]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3a
as a colorless oil (90 mg, yield = 92%). 1H NMR (400 MHz, CDCl3, TMS):
δ (ppm) 8.00 (s, 1H), 7.76-7.78 (m, 1H), 7.30-7.45 (m, 6H), 7.18-7.23 (m,
2H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 142.8, 141.2, 135.2,
132.6, 128.9, 126.9, 122.9, 122.6, 121.7, 119.4, 109.4. HRMS (ESI) m/z
[M+H]+ Calcd for C13H11N2 (195.0917), found: 195.0915.
1-(4-fluorophenyl)-1H-benzo[d]imidazole (3b) [9e]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3b
as a white soild (78 mg, yield = 74%). mp: 112-116 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 7.98 (s, 1H), 7.78-7.81 (m, 1H), 7.36-7.41 (m,
3H), 7.24-7.28 (m, 2H), 7.16-7.20 (m, 2H). 13C NMR (100 MHz, CDCl3,
TMS): δ (ppm) 160.9 (d, J = 247.0 Hz), 142.8, 141.2, 132.8, 131.3 (d, J =
3.0 Hz), 125.0 (d, J = 8.0 Hz), 122.8, 121.8, 119.6, 116.0 (d, J = 23.0 Hz),
109.1. HRMS (ESI) m/z [M+H]+ Calcd for C13H10FN2 (213.0823), found:
213.0826.
Conclusions
In summary, we reported herein a chemoselective, desulfurative
Chan-Lam coupling by using inexpensive and commercially
available arylboronic acids and benzimidazoline-2-thiones. This
expanded research together with our previous work[11] affords a
useful protocol for the chemoselective formation of N-
arylbenzimidazoles, S-arylbenzimidazoles, as well as N,S-
1-(4-chlorophenyl)-1H-benzo[d]imidazole (3c) [9a]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3c
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10.1002/ejoc.202000075
European Journal of Organic Chemistry
FULL PAPER
as a white soild (56 mg, yield = 49%). mp: 108-110 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.00 (s, 1H), 7.79-7.81 (m, 1H), 7.46-7.48 (m,
2H), 7.36-7.42 (m, 3H), 7.24-7.29 (m, 2H). 13C NMR (100 MHz, CDCl3,
TMS): δ (ppm) 142.9, 141.0, 133.8, 132.8, 132.5, 129.2, 124.2, 122.9,
122.0, 119.7, 109.1. HRMS (ESI) m/z [M+H]+ Calcd for C13H10ClN2
(229.0527), found: 229.0521.
1-(3,5-dimethylphenyl)-1H-benzo[d]imidazole (3i) [18c]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3i
as a yellow oil (75 mg, yield = 68%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 8.00 (s, 1H), 7.77-7.79 (m, 1H), 7.43-7.46 (m, 1H), 7.21-7.25 (m,
2H), 7.02 (d, J=12 Hz, 3H), 2.33 (s, 6H). 13C NMR (100 MHz, CDCl3,
TMS): δ (ppm) 142.9, 141.3, 138.9, 135.1, 132.7, 128.6, 122.4, 121.6,
120.6, 119.4, 109.6, 20.2. HRMS (ESI) m/z [M+H]+ Calcd for C15H15N2
(223.1230), found: 223.1235.
1-(4-bromophenyl)-1H-benzo[d]imidazole (3d) [9a]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3d
as a white soild (99 mg, yield = 79%). mp: 100-104 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 7.98 (s, 1H), 7.77-7.81 (m, 1H), 7.58-7.62 (m,
2H), 7.38-7.41 (m, 1H), 7.22-7.31 (m, 4H). 13C NMR (100 MHz, CDCl3,
TMS): δ (ppm) 142.9, 140.9, 134.3, 132.3, 132.2, 124.4, 122.9, 122.0,
120.5, 119.7, 109.1. HRMS (ESI) m/z [M+H]+ Calcd for C13H10BrN2
(273.0022), found: 273.0027.
1-(2,4-dimethylphenyl)-1H-benzo[d]imidazole (3j)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3j
as a yellow oil (57 mg, yield = 51%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 7.86 (s, 1H), 7.79-7.86 (m, 1H), 7.04-7.26 (m, 6H), 2,35 (s, 3H),
1.97 (s, 3H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 142.2, 142.1,
138.3, 134.0, 133.8, 131.0, 126.7, 126.4, 122.4, 121.3, 119.2, 109.5,
20.1, 16.4. HRMS (ESI) m/z [M+H]+ Calcd for C15H15N2 (223.1230),
found: 223.1236.
1-(3-bromophenyl)-1H-benzo[d]imidazole (3e) [18a]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3e
as a white soild (94 mg, yield = 69%). mp: 98-100 oC. 1H NMR (400 MHz,
CDCl3, TMS): δ (ppm) 8.00 (s, 1H), 7.76-7.81 (m, 1H), 7.59-7.60 (m, 1H),
7.48-7.51 (m, 1H), 7.41-7.45 (m, 1H), 7.32-7.38 (m, 2H), 7.23-7.28 (m,
2H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 142.9, 140.9, 136.4,
132.2, 130.3, 130.0, 125.9, 123.0, 122.4, 122.0, 121.4, 119.7, 109.2.
HRMS (ESI) m/z [M+H]+ Calcd for C13H10BrN2 (273.0022), found:
273.0025.
1-(3,4-dimethylphenyl)-1H-benzo[d]imidazole (3k) [18b]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3k
as a yellow oil (91 mg, yield = 82%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 7.99 (s, 1H), 7.76-7.80 (m, 1H), 7.41-7.45 (m, 1H), 7.71-7.26 (m,
5H), 2.27 (s, 6H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 142.8,
141.3, 137.5, 135.7, 132.9, 132.8, 129.9, 124.1, 122.4, 120.3, 119.4,
109.5, 18.8, 18.4. HRMS (ESI) m/z [M+H]+ Calcd for C15H15N2
(223.1230), found: 223.1234.
1-(3,5-difluorophenyl)-1H-benzo[d]imidazole (3f)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3f
as a white soild (86 mg, yield = 75%). mp: 84-86 oC. 1H NMR (400 MHz,
CDCl3, TMS): δ (ppm) 8.01 (s, 1H), 7.77-7.81 (m, 1H), 7.47-7.51 (m, 1H),
7.26-7.30 (m, 2H), 6.98-7.05 (m, 2H), 6.80-6.86 (m, 1H). 13C NMR (100
MHz, CDCl3, TMS): δ (ppm) 162.7 (dd, J = 250.0 Hz, J = 14.0 Hz), 143.1,
140.6, 137.4 (t, J = 12.0 Hz), 131.9, 123.3, 122.4, 119.9, 109.2, 106.1 (d,
J = 28.0 Hz), 102.4 (t, J = 25.0 Hz). HRMS (ESI) m/z [M+H]+ Calcd for
C13H9F2N2 (271.0728), found: 231.0729.
1-(4-ethylphenyl)-1H-benzo[d]imidazole (3l) [18e]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3l
as a yellow oil (87 mg, yield = 78%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 8.00 (s, 1H), 7.76-7.80 (m, 1H), 7.40-7.43 (m, 1H), 7.27-7.32 (m,
4H), 7.20-7.25 (m, 2H), 2.62-2.68 (m, 2H), 1.21 (t, J = 8.0 Hz, 3H). 13C
NMR (100 MHz, CDCl3, TMS): δ (ppm) 143.3, 142.8, 141.3, 132.8, 132.8,
128.3, 123.0, 122.5, 121.6, 119.4, 27.4, 14.4. HRMS (ESI) m/z [M+H]+
Calcd for C15H15N2 (223.1230), found: 223.1236.
1-(3,5-dichlorophenyl)-1H-benzo[d]imidazole (3g)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3g
as a white soild (65 mg, yield = 50%). mp: 162-164 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 7.99 (s, 1H), 7.78-7.80 (m, 1H), 7.43-7.46 (m,
1H), 7.36-7.37 (m, 3H), 7.25-7.30 (m, 2H). 13C NMR (100 MHz, CDCl3,
TMS): δ (ppm) 143.0, 140.6, 137.0, 135.4, 131.9, 127.0, 123.2, 122.3,
119.9, 109.1. HRMS (ESI) m/z [M+H]+ Calcd for C13H9Cl2N2 (263.0173),
found: 263.0177.
1-(4-isopropylphenyl)-1H-benzo[d]imidazole (3m)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3m
1
as a yellow oil (110 mg, yield = 93%). H NMR (400 MHz, CDCl3, TMS):
δ (ppm) 7.98 (s, 1H), 7.76-7.79 (m, 1H), 7.42-7.43 (m, 1H), 7.30 (s, 4H),
7.19-7.22 (m, 2H), 2.87-2.96 (m, 1H), 1.21 (d, J = 8.0 Hz, 6H). 13C NMR
(100 MHz, CDCl3, TMS): δ (ppm) 147.8, 142.8, 141.3, 132.8, 132.7,
126.9, 122.9, 122.4, 121.5, 119.4, 109.4, 32.7, 22.9. HRMS (ESI) m/z
[M+H]+ Calcd for C16H16N2 (236.1313), found: 236.1311.
1-(o-tolyl)-1H-benzo[d]imidazole (3h) [9e]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3h
as a yellow oil (72 mg, yield = 69%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 7.88 (s, 1H), 7.79-7.81 (m, 1H), 7.32-7.37 (m, 2H), 7.17-7.29 (m,
4H), 7.03-7.06 (m, 1H), 2.01 (s, 3H). 13C NMR (100 MHz, CDCl3, TMS): δ
(ppm) 142.2, 141.9, 134.3, 133.7, 133.6, 130.4, 128.3, 126.6, 126.1,
122.4, 121.4, 119.3, 109.4, 16.5. HRMS (ESI) m/z [M+H]+ Calcd for
C14H13N2 (209.1073), found: 209.1074.
1-(4-methoxyphenyl)-1H-benzo[d]imidazole (3n) [9e]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3n
as a yellow oil (98 mg, yield = 88%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 8.05 (s, 1H), 7.86-7.88 (m, 1H), 7.39-7.46 (m, 3H), 7.28-7.35 (m,
2H), 7.05-7.08 (m, 2H) 3.88 (m, 3H). 13C NMR (100 MHz, CDCl3, TMS): δ
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000075
European Journal of Organic Chemistry
FULL PAPER
(ppm) 159.3, 143.8, 142.5, 134.2, 129.1, 125.7, 123.5, 122.6, 120.4,
115.1, 110.3, 55.6. HRMS (ESI) m/z [M+H]+ Calcd for C14H13N2O
(225.1022), found: 225.1027.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3t
as a yellow oil (87 mg, yield = 71%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 8.20 (s, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.89-7.94 (m, 4H), 7.55-7.62
(m, 4H), 7.32-7.38 (m, 2H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm)
144.1, 142.4, 133.9, 133.7, 133.6, 132.4, 130.2, 127.9, 127.9, 127.3,
126.8, 123.7, 122.9, 122.2, 122.1, 120.6, 110.5. HRMS (ESI) m/z [M+H]+
Calcd for C17H13N2 (245.1073), found: 245.1075.
1-(4-ethoxyphenyl)-1H-benzo[d]imidazole (3o)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3o
1
as a yellow oil (106 mg, yield = 89%). H NMR (400 MHz, CDCl3, TMS):
5,6-dimethyl-1-phenyl-1H-benzo[d]imidazole (3u) [18d]
δ (ppm) 8.04 (s, 1H), 7.84-7.89 (m, 1H), 7.43-7.46 (m, 1H), 7.37-7.39 (m,
2H), 7.29-7.32 (m, 2H), 7.03-7.07 (m, 2H), 4.07-4.12 (m, 2H) 1.46 (t, J
=8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 158.7, 143.8,
142.5, 134.2, 128.9, 125.7, 123.5, 122.5, 120.4, 115.6, 110.3, 63.9, 14.7.
HRMS (ESI) m/z [M+H]+ Calcd for C15H15N2O (239.1179), found:
239.1172.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3u
as a yellow oil (82 mg, yield = 74%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 8.01 (s, 1H), 7.63 (s, 1H), 7.53-7.57 (m, 2H), 7.41-7.50 (m, 3H),
7.30-7.38 (s, 1H), 2.36 (t, J = 12.0 Hz, 6H). 13C NMR (100 MHz, CDCl3,
TMS): δ (ppm) 142.5, 141.5, 136.6, 132.9, 132.1, 131.7, 129.9, 127.7,
123.8, 120.4, 110.5, 20.5, 20.2. HRMS (ESI) m/z [M+H]+ Calcd for
C15H15N2 (223.1230), found: 223.1233.
1-(benzo[d][1,3]dioxol-5-yl)-1H-benzo[d]imidazole (3p)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3p
1
1-(4-fluorophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3v)
as a yellow oil (117 mg, yield = 98%). H NMR (400 MHz, CDCl3, TMS):
δ (ppm) 8.03 (s, 1H), 7.85-7.87 (m, 1H), 7.45-7.47 (m, 1H), 7.29-7.34 (m,
2H), 6.93-6.96 (m, 3H), 6.07 (s, 2H). 13C NMR (100 MHz, CDCl3, TMS): δ
(ppm) 148.7, 147.5, 143.7, 142.4, 143.0, 130.1, 123.6, 122.7, 120.5,
117.8, 110.3, 108.8, 105.7, 102.0. HRMS (ESI) m/z [M+H]+ Calcd for
C14H11N2O2 (239.0815), found: 239.0818.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3v
as a yellow oil (67 mg, yield = 56%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 7.95 (s, 1H), 7.62 (s, 1H), 7.44-7.47 (m, 2H), 7.22-7.27 (m, 3H),
2.38 (d, J = 8.0 Hz, 6H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm)
161.8 (d, J = 247.0 Hz）, 142.4, 141.4, 133.1, 132.7 (d, J = 3.0 Hz),
132.4, 131.8, 125.8 (d , J = 9.0 Hz), 120.5, 116.9 (d, J = 23.0 Hz), 110.2,
20.5, 20.2. HRMS (ESI) m/z [M+H]+ Calcd for C15H14FN2 (241.1136),
found: 241.1138.
methyl 4-(1H-benzo[d]imidazol-1-yl)benzoate (3q) [18d]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3q
as a white soild (89 mg, yield = 70%). mp: 100-104 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.26 (d, J = 8.0 Hz, 2H), 8.17 (s, 1H), 7.88-
7.90 (m, 1H), 7.58-7.63 (m, 3H), 7.35-7.38 (m, 2H), 3.98 (s, 3H). 13C
NMR (100 MHz, CDCl3, TMS): δ (ppm) 166.0, 144.2, 141.9, 140.1, 133.1,
131.6, 129.4, 124.1, 123.2, 123.2, 120.8, 110.4, 52.4. HRMS (ESI) m/z
[M+H]+ Calcd for C15H13N2O2 (253.0972), found: 253.0978.
1-(4-chlorophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3w) [18d]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3w
as a yellow solid (58 mg, yield = 45%). mp: 116-118 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 7.79 (s, 1H), 7.63 (s, 1H), 7.53 (d, J = 8.0 Hz,
2H), 7.44 (d, J = 8.0 Hz, 2H), 7.26 (s, 1H), 2.39 (d, J = 12.0 Hz, 6H). 13
C
4-(1H-benzo[d]imidazol-1-yl)benzonitrile (3r) [10a]
NMR (100 MHz, CDCl3, TMS): δ (ppm) 142.6, 141.2, 135.2, 133.5, 133.2,
132.0, 132.0, 130.2, 125.1, 120.6, 110.3, 20.6, 20.2. HRMS (ESI) m/z
[M+H]+ Calcd for C15H14ClN2 (257.0840), found: 257.0846.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3r
as a white soild (87 mg, yield = 79%). mp: 112-114 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.18 (s, 1H), 7.89-7.91 (m, 3H), 7.68-7.70 (m,
2H), 7.57-7.60 (m, 1H), 7.38-7.40 (m, 2H). 13C NMR (100 MHz, CDCl3,
TMS): δ (ppm) 144.3, 141.6, 140.1, 134.2, 133.0, 132.8, 129.1, 124.5,
123.9, 123.6, 121.0, 117.8, 111.5, 110.2. HRMS (ESI) m/z [M+H]+ Calcd
for C14H10N3 (220.0869), found: 220.0866.
1-(3,5-dichlorophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3x)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3x
as a yellow solid (76 mg, yield = 52%). mp: 99-102 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 7.91 (s, 1H), 7.53 (s, 1H), 7.36 (s, 3H), 7.21
(t, J = 12.0 Hz, 1H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 206.1,
141.3, 139.8, 137.3, 135.3, 132.7, 131.5, 126.7, 121.0, 119.6, 109.2,
19.6, 19.2. HRMS (ESI) m/z [M+H]+ Calcd for C15H12Cl2N2 (290.0378),
found: 259.0377.
1-(naphthalen-1-yl)-1H-benzo[d]imidazole (3s) [9e]
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3s
as a colorless oil (76 mg, yield = 62%). 1H NMR (400 MHz, CDCl3, TMS):
δ (ppm) 8.12 (s, 1H), 7.94-8.04 (m, 3H), 7.53-7.62 (m, 3H), 7.40-7.46 (m,
2H), 7.33-7.37 (m, 1H), 7.22-7.26 (m, 1H), 7.09 (d, J = 8.0 Hz, 1H). 13C
NMR (100 MHz, CDCl3, TMS): δ (ppm) 143.7, 143.3, 134.4, 129.6, 128.4,
127.5, 120.7, 125.4, 124.9, 123.6, 122.7, 122.5, 120.4, 110.8. HRMS
(ESI) m/z [M+H]+ Calcd for C17H13N2 (245.1073), found: 245.1079.
1-(3,5-difluorophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3y)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3y
as a yellow solid (58 mg, yield = 45%). mp: 110-114 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 7.91 (s, 1H), 7.54 (s,1H), 7.26 (s, 1H), 7.01
(d, J = 12.0 Hz, 2H), 6.79-6.84 (m, 1H), 2.32 (s, 6H). 13C NMR (100 MHz,
CDCl3, TMS): δ (ppm) 162.6 (dd, J = 249.0 Hz, J = 14.0 Hz), 141.6,
139.8, 137.7 (t, J = 12.0 Hz), 132.6, 131.4, 130.3, 119.8, 109.3, 105.8 (d,
1-(naphthalen-2-yl)-1H-benzo[d]imidazole (3t) [9n]
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000075
European Journal of Organic Chemistry
FULL PAPER
J = 28.0 Hz), 102.0 (t, J = 26.0 Hz), 19.6, 19.2. HRMS (ESI) m/z [M+H]+
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
Calcd for C15H13F2N2 (259.1041), found: 259.1042.
was isolated by column (PE/EA = 2:1) to give the intended compound
1
3ze as a yellow solid (94 mg, yield = 82%). mp: 78-80 oC. H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.03 (s, 1H), 7.48-7.55 (m, 3H), 7.36-7.43 (m,
3H), 7.18-7.23 (m, 1H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 156.1,
147.8 (dd, J = 243.0 Hz, J = 16.0 Hz), 147.1 (dd, J = 240.0 Hz, J = 16.0
Hz), 142.5 (d, J = 2.0 Hz), 138.0 (d. J = 12.0 Hz), 134.6, 129.2, 127.6,
122.8, 118.6, 114.6, 106.7 (d, J = 20.0 Hz), 97.5 (d, J = 23.0 Hz). HRMS
(ESI) m/z [M+H]+ Calcd for C13H9F2N2 (231.0728), found: 231.0723.
5,6-dimethyl-1-(o-tolyl)-1H-benzo[d]imidazole (3z)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3z
as a yellow oil (53 mg, yield = 45%). 1H NMR (400 MHz, CDCl3, TMS): δ
(ppm) 7.78 (s, 1H), 7.56 (s, 1H), 7.33-7.35 (m, 2H), 7.26-7.30 (m, 1H),
7.20 (t, J = 8.0 Hz, 1H), 6.82 (s, 1H), 2.32 (s, 3H), 2.25 (s, 3H), 2.02 (s,
3H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 141.1, 140.8, 134.3,
134.0, 132.2, 131.7, 130.4, 130.4, 128.1, 126.4, 126.0, 119.2, 109.5,
19.4, 19.2, 16.6. HRMS (ESI) m/z [M+H]+ Calcd for C16H17N2 (237.1386),
found: 237.1385.
5,6-difluoro-1-(4-isopropylphenyl)-1H-benzo[d]imidazole (3zf)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3zf
as a white solid (94 mg, yield = 85%). mp: 136-138 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.00 (s, 1H), 7.51-7.55 (m, 1H), 7.35 (d, J =
8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.19-7.23 (m, 1H), 2.90-2.97 (m,
1H), 1.24 (d, J = 8.0 Hz, 6H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm)
148.6, 147.7 (dd, J = 243.0Hz, J = 15.0 Hz), 147.1 (dd, J = 241.0Hz, J =
15.0 Hz),142.6, 138.0 (d, J = 10.0 Hz), 132.3, 128.3 (d, J = 10.0 Hz),
127.1, 122.9, 106.6(d, J = 20.0 Hz), 97.5 (d, J = 24.0 Hz), 32.8, 22.8.
HRMS (ESI) m/z [M+H]+ Calcd for C16H15F2N2 (273.1198), found:
273.1193.
1-(3,5-dimethylphenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3za)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3za as a yellow oil (73 mg, yield = 58%). 1H NMR (400 MHz, CDCl3,
TMS): δ (ppm) 7.90 (s, 1H), 7.53 (s, 1H), 7.21 (s, 1H), 7.00(d, J = 12.0
Hz, 3H), 2.31 (t, J = 8.0 Hz, 12H). 13C NMR (100 MHz, CDCl3, TMS): δ
(ppm) 141.4, 140.6, 138.8, 135.4, 131.6, 130.5, 128.3, 120.5, 119.3,
109.6, 20.3, 19.5, 19.2. HRMS (ESI) m/z [M+H]+ Calcd for C17H19N2
(251.1543), found: 251.1545.
5,6-difluoro-1-(4-methoxyphenyl)-1H-benzo[d]imidazole (3zg)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3zg as a white solid (78 mg, yield = 60%). mp: 130-132 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 7.96 (s, 1H), 7.50-7.55 (m, 1H), 7.28 (d, J =
8.0 Hz, 2H), 7.10-7.15 (m, 1H), 7.00 (d, J = 12.0 Hz, 2H), 3.81 (s, 3H).
13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 158.6, 147.7 (dd, J = 243.0
Hz, J = 16.0 Hz), 147.0 (dd, J = 240.0 Hz, J = 15.0 Hz), 142.8, 137.8 (d, J
= 10.0 Hz), 128.6 (d, J = 11.0 Hz), 127.4, 124.6, 114.2, 106.6 (d, J = 19.0
Hz), 97.3 (d, J = 23.0 Hz), 54.6. HRMS (ESI) m/z [M+H]+ Calcd for
C14H11F2N2O (261.0834), found: 261.0838.
1-(4-isopropylphenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3zb)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3zb as a yellow oil (73 mg, yield = 55%). 1H NMR (400 MHz, CDCl3,
TMS): δ (ppm) 7.89 (s, 1H), 7.54 (s, 1H), 7.32 (s, 4H), 7.22 (s, 1H), 2.89-
2.95 (m, 1H), 2.30 (d, J = 12.0 Hz, 6H), 1.23 (d, J = 8.0 Hz, 6H). 13C
NMR (100 MHz, CDCl3, TMS): δ (ppm) 147.6, 141.5, 140.5, 133.2, 131.7,
131.3, 130.5, 126.8, 122.8, 119.3, 109.6, 32.8, 22.9, 19.5, 19.2. HRMS
(ESI) m/z [M+H]+ Calcd for C18H21N2 (265.1699), found: 265.1696.
1-(3,5-difluorophenyl)-5,6-difluoro-1H-benzo[d]imidazole (3zh)
1-(4-methoxyphenyl)-5,6-dimethyl-1H-benzo[d]imidazole (3zc)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3zh as a white solid (98 mg, yield = 74%). mp: 156-158 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.04 (s, 1H), 7.54-7.58 (m, 1H), 7.26-7.30 (m,
1H), 6.98-7.01 (m, 2H), 6.86-6.92 (m, 1H). 13C NMR (100 MHz, CDCl3,
TMS): δ (ppm) 168.2 (dd, J = 250.0 Hz, J = 15.0 Hz), 148.1 (dd, J =
245.0 Hz, J = 14.0 Hz), 147.4 (dd, J = 242.0 Hz, J = 15.0 Hz), 141.9 (d, J
= 3.0 Hz), 138.3 (d, J = 10.0 Hz), 136.7 (t, J = 13.0 Hz), 127.3 (d, J =
11.0 Hz), 107.3 (d, J = 19.0 Hz), 106.2 (d, J = 29.0 Hz), 103.1 (t, J = 25.0
Hz), 97.5 (d, J = 24.0 Hz). HRMS (ESI) m/z [M+H]+ Calcd for C13H7F4N2
(267.0540), found: 267.0541.
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3zc as a yellow oil (66 mg, yield = 53%). 1H NMR (400 MHz, CDCl3,
TMS): δ (ppm) 7.86 (s. 1H), 7.53 (s, 1H), 7.31 (d, J = 12.0 Hz, 2H), 7.14
(s, 1H), 6.98 (d, J = 12.0 Hz, 2H), 3.80 (s, 3H), 2.29 (d, J = 16.0 Hz, 6H).
13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 158.1, 141.3, 140.7, 131.7,
131.7, 130.4, 128.4, 124.5, 119.3, 114.0, 109.4, 54.6, 19.5, 19.2. HRMS
(ESI) m/z [M+H]+ Calcd for C16H17N2O (253.1335), found: 253.1335.
5,6-dimethyl-1-(naphthalen-1-yl)-1H-benzo[d]imidazole (3zd)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3zd as a yellow oil (50 mg, yield = 36%). 1H NMR (400 MHz, CDCl3,
TMS): δ (ppm) 7,89-7.94 (m, 3H), 7.61 (s, 1H), 7.43-7.54 (m, 3H), 7.36 (d,
J = 4.0 Hz, 2H), 6.79 (s, 1H), 2.32 (s, 3H), 2.18 (s, 3H). 13C NMR (100
MHz, CDCl3, TMS): δ (ppm) 142.0, 140.8, 133.7, 133.3, 131.8, 131.6,
130.6, 128.8, 128.4, 127.3, 126.4, 125.9, 124.4, 123.8, 121.6, 119.3,,
109.8, 19.4, 19.2. HRMS (ESI) m/z [M+H]+ Calcd for C19H17N2
(273.1386), found: 273.1389.
5,6-difluoro-1-(naphthalen-1-yl)-1H-benzo[d]imidazole (3zi)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3zi
as a yellow solid (91 mg, yield = 65%). mp: 144-146 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.10 (s, 1H), 7.95 (d, J = 12.0 Hz, 1H), 7.79-
7.86 (m, 3H), 7.43-7.57 (m, 4H), 7.23-7.27 (m, 1H). 13C NMR (100 MHz,
CDCl3, TMS): δ (ppm) 147.8 (dd, J = 243.0 Hz, J = 16.0 Hz), 147.1 (dd, J
= 241.0 Hz, J = 15.0 Hz), 142.7, 138.2 (d, J = 11.0 Hz), 132.5, 132.0,
131.6, 129.4, 128.2 (d, J = 10.0 Hz), 126.9 (d, J = 10.0 Hz), 126.5, 126.1,
121.1, 120.7, 106.8 (d, J = 19.0 Hz), 97.7, 97.4. HRMS (ESI) m/z [M+H]+
Calcd for C17H11F2N2 (281.0885), found: 281.0883.
5,6-difluoro-1-phenyl-1H-benzo[d]imidazole (3ze)
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202000075
European Journal of Organic Chemistry
FULL PAPER
5,6-dichloro-1-phenyl-1H-benzo[d]imidazole (3zj)
Laboratory for the Synthesis and Application of Organic
Functional Molecules, Hubei University (KLSAOFM1810),
Science and Technology Department of Hubei Province
(2019CFB596), Key Laboratory of Hubei Province for Coal
Conversion and New Carbon Materials (WKDM202003) are all
greatly appreciated. J.-Q. C. thanks the support of Postgraduate
Innovation Foundation from Wuhan Institute of Technology
(CX2019170).
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3zj
as a white solid (130 mg, yield = 98%). mp: 120-124 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.03 (s, 1H), 7.85 (s, 1H), 7.51 (t, J = 8.0 Hz,
3H), 7.37-7.43 (m, 3H). 13C NMR (100 MHz, CDCl3, TMS): δ (ppm) 134.4,
129.2, 127.6, 126.8, 125.9, 122.9, 120.6, 110.9. HRMS (ESI) m/z [M+H]+
Calcd for C13H9Cl2N2 (263.0173), found: 263.0175.
5,6-dichloro-1-(4-ethylphenyl)-1H-benzo[d]imidazole (3zk) [18e]
Keywords: Chemoselective
Coupling • C-N Bond
•
Desulfurative
•
Chan-Lam
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3zk as a white solid (84 mg, yield = 58%). mp: 120-122 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 8.01 (s, 1H), 7.86 (s, 1H), 7.52 (s, 1H), 7.28-
7.34 (m, 4H), 2.65-2.71 (m, 2H), 1.23 (t, J = 8.0 Hz, 3H). 13C NMR (100
MHz, CDCl3, TMS): δ (ppm) 144.1, 143.1, 142.1, 132.1, 132.0, 128.6,
126.7, 125.8, 123.0, 120.6, 110.9, 27.5, 14.4. HRMS (ESI) m/z [M+H]+
Calcd for C15H13Cl2N2 (291.0540), found: 291.0545.
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5,6-dichloro-1-(4-ethoxyphenyl)-1H-benzo[d]imidazole (3zl)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound 3zl
as a white solid (63 mg, yield = 41%). mp: 138-140 oC. 1H NMR (400
MHz, CDCl3, TMS): δ (ppm) 7.97 (s, 1H), 7.85 (s, 1H), 7.45 (s, 1H), 7.23
(d, J = 8.0 Hz, 2H), 6.98-7.00 (m, 2H), 4.01-4.06 (m, 2H). 13C NMR (100
MHz, CDCl3, TMS): δ (ppm) 158.1, 143.3, 141.9, 132.5, 126.9, 126.7,
125.7, 124.6, 120.5, 114.8, 110.8, 62.9, 13.7. HRMS (ESI) m/z [M+H]+
Calcd for C15H13Cl2N2O (307.0399), found: 307.0396.
[2]
[3]
[4]
5,6-dichloro-1-(4-fluorophenyl)-1H-benzo[d]imidazole (3zm)
Based on THE ABOVE MENTIONED PROCEDURE, the crude material
was isolated by column (PE/EA = 2:1) to give the intended compound
3zm as a white solid (63 mg, yield = 45%). mp: 210-214 oC. 1H NMR
(400 MHz, CDCl3, TMS): δ (ppm) 8.00 (s, 1H), 7.88 (s, 1H), 7.47 (s, 1H),
7.37-7.41 (m, 2H), 7.19-7.25 (m, 2H). 13C NMR (100 MHz, CDCl3, TMS):
δ (ppm) 161.3 (d, J = 249.0 Hz), 142.9, 142.0, 132.1, 130.4, 127.1, 126.1,
125.1 (d, J = 8.0 Hz), 120.8, 116.3 (d, J = 23.0 Hz), 110.6. HRMS (ESI)
m/z [M+H]+ Calcd for C13H8Cl2FN2 (281.0043), found: 281.0048.
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Based on THE ABOVE MENTIONED PROCEDURE, the crude material
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3zn as a colorless oil (69 mg, yield = 44%). 1H NMR (400 MHz, CDCl3,
TMS): δ (ppm) 8.05 (s, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7,94 (d, J = 4.0 Hz,
2H), 7.51-7.57 (m, 2H), 7.39-7.47 (m, 2H), 7.25 (d, J = 8.0 Hz, 1H), 7.12
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133.4, 130.3, 129.2, 128.4, 127.6, 126.9, 126.9, 126.2, 126.0, 124.4,
123.9, 120.9, 120.6, 111.1. HRMS (ESI) m/z [M+H]+ Calcd for
C17H11Cl2N2 (313.0294), found: 313.0298.
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European Journal of Organic Chemistry
FULL PAPER
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Key Topic*
Author(s), Corresponding Author(s)*
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Title
((Insert TOC Graphic here: max.
width: 5.5 cm; max. height: 5.0 cm;
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Key Topic*: Chan-Lam Coupling
Jin-Quan Chen, Xing Liu, Jia Guo, and
Zhi-Bing Dong *
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A Chemoselective and Desulfurative
Chan-Lam Coupling: C-N Bond
Formation between Benzimidazoline-
2-Thiones and Arylboronic Acids
Text for Table of Contents (about 350 characters)
*one or two words that highlight the emphasis of the paper or the field of the study
An efficient method for the chemoselective and desulfurative Chan-Lam cross-coupling was developed. By modulating the
amount of the catalyst Cu(OAc)2•H2O, alkali, temperature and solvent, the desulfurative C-N bond formation product (N-
arylbenzimidazoles) could be selectively furnished smoothly. The features of this protocol are the use of inexpensive and
readily available catalyst, ligand-free condition, wide substrate scope, easy performance, giving the C-N cross-coupling
products in moderate to excellent yields. It shows potential synthetic value for the preparation of a diversity of
arylbenzoheterocyclic compounds which are potentially active in pharmaceuticals and agrochemicals.
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