Synthesis of Benzimidazoles through Palladium-Catalyzed Amination of 2-Iodobenzimines with Diaziridinone

Article abstract of DOI:10.1002/adsc.201801367

An efficient approach for the synthesis of benzimidazoles has been developed through the Pd-catalyzed amination of 2-iodobenzimines with diaziridinone. A wide range of 2-(hetero)aryl benzimidazloes are synthesized in good to excellent yields. The reactions likely involve C,C-palladacycles derived from 2-iodobenzimines as the key intermediate, and the palladacycles reacted with diaziridinone to form benzimidazoles. (Figure presented.).

Full text of DOI:10.1002/adsc.201801367

Title: Synthesis of Benzimidazoles through Palladium-Catalyzed
Amination of 2-Iodobenzimines with Diaziridinone
Authors: Ding Ma, Xiaoming Ji, Zhuo Wu, Cang Cheng, Bo Zhou, and
Yanghui Zhang
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10.1002/adsc.201801367
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Synthesis of Benzimidazoles through Palladium-Catalyzed
Amination of 2-Iodobenzimines with Diaziridinone
Ding Ma,a Xioming Ji,a Zhuo Wu,a Cang Cheng,a Bo Zhou,a Yanghui Zhanga, *
a
School of Chemical Science and Engineering, Shanghai Key Laboratory of Chemical Assessment and Sustainability,
Tongji University, 1239 Siping Road, Shanghai 200092, P. R. China
E-mail: zhangyanghui@tongji.edu.cn; Web: http://zhangyhgroup.tongji.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. An efficient approach for the synthesis of benzimidazoles has been developed through the Pd-catalyzed amination
of 2-iodobenzimines with diaziridinone. A wide range of 2-(hetero)aryl benzimidazloes are synthesized in good to excellent
yields. The reactions likely involve C,C-palladacycles derived from 2-iodobenzimines as the key intermediate, and the
palladacycles reacted with diaziridinone to form benzimidazoles.
Keywords: Palladacycles; C–H activation; Amination; Palladium; Benzimidazole.
Introduction
Benzimidazoles are ubiquitous structural motifs in
naturally occurring compounds.[1] More importantly,
this class of N-containing heterocycles may exhibit
remarkable biological activities such as anticancer
and
antimicrobial
activity.[2]
Consequently,
benzimidazoles are popular and crucial core
structures in drug discovery and have successfully
been developed into pharmaceuticals.[3] Furthermore,
they have also found extensive applications in
materials science.[4] It is not surprising that
developing synthetic methods for benzimidazoles has
been the subject of intensive research, and a number
of synthetic reactions have been developed.[5]
Traditionally, benzimidazoles are synthesized by the
condensation of 1, 2-diaminoarenes with carbonyl
derivatives.[6] A strategy involving transition-metal-
catalyzed C–N bond formation represents a relatively
modern approach.[7]
C,C-palladacycles are an important class of
metallacycles. C,C-palladacycles consist of two C-Pd
bonds, and the two C–Pd bonds can be utilized to
develop new transformations.[8] A variety of C,C-
palladacycles are available, including those consisting
of a C(sp2)–Pd–C(sp2) or C(sp2)–Pd–C(sp3) bonding
motif, and quite a few novel reactions have been
developed by capitalizing on the unique reactivity
and structures of these palladacycles.[9] Our group has
been interested in C,C-palladacycles, and developed
some synthetically useful reactions through
intermolecular functionalization of this unique class
of palladacycles recently.[10]
Scheme 1. Reactions of Imino-Containing C,C-
Palladacycles Derived from 2-Iodobenzimines and
Amination Reactions of C,C-Palladacycles with Di-tert-
Butyldiaziridinone .
1
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10.1002/adsc.201801367
Advanced Synthesis & Catalysis
Table 1. Optimization of Reaction Conditions.
The majority of the current C,C-palladacycles
consist of two aryl C-Pd bonds. It is desirable to
study other types of C,C-palladacycles and develop
their reactions. In 2007, the Larock group reported a
novel aryl to imidoyl palladium migration reaction of
2-iodobenzimine derivatives (Scheme 1).[11a] This
reaction involved a five-membered C,C-palladacycle
as the intermediate. This palladacycle contains an
imino moiety and represents a new class of C,C-
palladacycles, and can be utilized to develop
synthetically useful reactions, in particular for N-
containing heterocycles. However, this C,C-
palladacycle has not been exploited to develop other
organic reactions.[11b, c, d] On the other hand, the Shi
group demonstrated that diaziridinone exhibits high
reactivity towards C,C-palladacycles (Scheme 1).[12a,
entry
1[b]
2
3
4
Base (equiv.) temperature (oC) yield (%)[a]
KOAc (2.0)
\
110
110
110
110
135
135
135
135
135
135
135
14
20
KOAc (2.0)
KOPiv (2.0)
KOPiv (2.0)
KOPiv (1.0)
KOPiv (0.5)
KOPiv (1.0)
KOPiv (1.0)
KOPiv (1.0)
KOPiv (1.0)
72
78
84
95
77
95
73
5
6
7
8[c]
9[d]
10[e]
b]
83
Inspired by this pioneering work, our group
11[c, f]
94 (91[g])
developed amination reactions of C,C-palladacycles
derived from 2-iodobiphenyls or formed through the
reaction of aryl iodides and alkynes (Scheme 1).[12c, d]
We envisioned that diaziridinone might also react
with the C,C-palladacycles derived from 2-
iodobenzimines. Herein, we report a protocol for the
Pd-catalyzed reaction of 2-iodobenzimines with
diaziridinone, which represents a new approach for
the construction of benzimidazoles.
[a]
1
The yields were determined by H NMR analysis of
crude reaction mixture using CH2Br2 as the internal
standard.
[b] No Cs2CO3.
[c] 1.5 equiv. of 1a.
[d] 1.0 equiv. of 1a.
[e] 5 mol % Pd(OAc)2.
[f] 3 h.
[g] Isolated yield.
Results and Discussion
After developing an efficient protocol for the
synthesis of benzimidazoles, we then explored its
We commenced our studies by investigating the
reaction of 2-iodobenzimine 1a with diaziridinone 2.
As shown in Table 1, in the presence of KOAc as a
base, the desired benzimidazole 3a was formed in
14% yield (entry 1), and a yield of 20% was obtained
by using 1 equivalent of Cs2CO3 (entry 2). Gratefully,
the yield was dramatically improved to 72% when a
combination of KOAc and Cs2CO3 was added (entry
3). Replacing KOAc with KOPiv resulted in a
slightly higher yield (entry 4), and the yield was
further enhanced to 84% by elevating the reaction
temperature (entry 5). Unexpectedly, a yield as high
as 95% was obtained when 1 equivalent of KOPiv
was used (entry 6). Further reducing the equivalents
of the base led to a lower yield (entry 7). The exact
roles of KOPiv and Cs2CO3 remain to be investigated.
They should be able to promote the generation of the
active Pd(0) species and C-H activation.[12c][13]
Notably, the yield remained to be excellent even
using 1.5 equivalents of 2 (entry 8). However, the
yield decreased when one equivalent of 2 was used
(entry 9). The desired product was still obtained in
85% yield in the presence of 5 mol% Pd(OAc)2 (entry
10). The reaction was completed in 3 hours and the
excellent yield was still obtained (entry 11).
substrate scope towards
a
variety of 2-
iodobenzimines. We first examined the compatibility
of functional groups on the iodo-bearing benzene
rings. As shown in Table 2, the electron-donating
methyl and methoxy groups were compatible and the
corresponding products were formed in excellent yields
(3b and 3c). The fluoro and chloro group were also well-
tolerated (3d and 3e). While the fluoro-substituted
benzimidazole was formed in an excellent yield, the
presence of a chloro group led to a moderate yield. As it
has been reported that P(o-tol)3 could promote the
functionalization reaction of C,C-palladacycles obtained
from aryl halides,[10d] we investigated the impact of the
ligand on this amination reaction. Gratefully, a 76% yield
was obtained by the addition of 20 mol% P(o-tol)3 as a
ligand. The substrates bearing
a typical electron-
withdrawing group such as trifluoromethyl, ester, and
cyano were also suitable, albeit in low yields (3f-3h).
Likewise, the yields could be improved by using ligand
P(o-tol)3. Benzimines bearing a methyl group on the
positions ortho or meta to the benzylideneamino group
also underwent the amination reaction, and the yields were
high (3i and 3j).
2
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10.1002/adsc.201801367
Advanced Synthesis & Catalysis
Table 2. Substrate Scope.[a]
The tert-butyl group of the resulting benzimidazole
products could be readily removed under acidic conditions
(Scheme 2).[14] The resulting free amine can be
manipulated, which allows easy access to a variety of 1-
substituted benzimidazole derivatives.
Scheme 2. Deprotection of the Benzimidazole Products.
Our reaction forms 2-arylbenzimidazoles as the products.
Notably, it has been reported that 2-arylbenzimidazoles
can be transformed into diverse polycyclic heterocycles
that are pharmacologically important or have potential
applications in materials science. As shown in Scheme 3,
2-phenyl benzimidazole 4a can react with o-
dibromobenzene
phenanthridines (A).[15a] 4a can also react with alkynes,
and the reaction yielded N-doped benzo-
[cd]fluoranthenium salts (B)[15b] or benzimidazole-fused
isoquinolines Furthermore,
(C).[15c]
to
form
N-heteroaryl-fused
benzoimidazoisoindoles can be easily accessed through
the reaction of 2-arylbenzimidazoles with alkenes (D).[15d]
[a] Isolated yield.
Scheme 3. Transformation of 2-Arylbenzimidazoles.
[b] 20 mol % P(o-tol)3 was added.
Next, we investigated the performance of substituents on
the other benzene ring. A range of substituents on the para
positions were compatible (3k-3r). The yields were good
or excellent for most of the substituents. Although the ester
and cyano groups gave lower yields, the yields could be
enhanced to over 90% by the addition of P(o-tol)3 (3q and
3r). The presence of substituents on the meta or ortho
positions did not affect the high efficiency of the
benzimidazole-forming reaction (3s-3w), and disubstituted
derivatives also exhibited excellent reactivity (3x and 3y).
Notably, the substrates containing an aromatic heterocycle
including furan, thiophene, and pyridine were also suitable
(3z-3ab). The corresponding benzimidazoles were formed
in good or excellent yields in the presence of P(o-tol)3.
Next, we investigated the kinetic isotope effect in this
amination reaction. Deuterated 2-iodobenzimine 1a-D6
was synthesized. When a mixture of 1a and 1a-D6 in a
ratio of 1:1 was subjected to the standard conditions and
the reaction was stopped in 15 minutes, the equal
quantities of 3a and 3a-D6 were formed (Scheme 4).
Therefore, the intermolecular KIE value was 1.0.
Furthermore, parallel reactions of 1a and 1a-D6 were also
carried out, and the KIE value was 1.1(Scheme 4). These
results indicate that C-H bond cleavage was not the
turnover-limiting step.
3
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10.1002/adsc.201801367
Advanced Synthesis & Catalysis
Conclusion
In conclusion, we have developed a new protocol for
the synthesis of benzimidazoles starting from 2-
iodobenzimines
Palladacycles
and
that
diaziridinones.
obtained
C,C-
through
are
intramolecular C−H activation of 2-iodobenzimines
act as the key intermediates. The palladacycles are
aminated with diaziridinone efficiently to yield
benzimidazoles. The reaction features broad substrate
scope and high yields. The resulting 2-(hetero)aryl
benzimidazloes can be transformed into biologically
important diverse polycyclic heterocycles.
Experimental Section
General Procedure for the Synthesis of Benzimidazoles.
A 25 mL Schlenk-type tube (with a Teflon screw cap and a
side arm) equipped with a magnetic stir bar was charged
with Pd(OAc)2 (2.3 mg, 0.01 mmol), Cs2CO3 (32.6 mg, 0.1
mmol), KOPiv (14.0 mg, 0.1 mmol), the corresponding
substrate (0.1 mmol), di-tert-butyldiaziridinone (25.5 mg,
0.15 mmol) and DMF (2 mL). The reaction tube was
evacuated and backfilled with nitrogen (5 times). The
Scheme 4. Kinetic Isotope Effect.
o
mixture was stirred at 135 C for 3 hours. After cooling to
room temperature, the reaction mixture was diluted with
EtOAc (15 mL), washed with saturated NaCl solution (3
times), dried over anhydrous Na2SO4 and concentrated in
vacuo. The residue was purified by preparative silica gel
TLC with PE/EA to give the corresponding products.
On the basis of the products formed in the reaction and
12]
the previous reports,[11,
we proposed a tentative
mechanism for the benzimidazole-forming reaction. As
shown in Scheme 5, the catalytic cycle starts with the
oxidative addition of 2-iodobenzimine to Pd(0) to generate
Pd(II) species A. The subsequent intramolecular C−H
activation affords palladacycle B. Next, B inserts into the
N−N bond of diaziridinone through oxidative addition to
provide pallada(IV)cycle C. C then undergoes reductive
elimination to give intermediate D-1 or D-2 (pathway a).
The subsequent β-N elimination and reductive elimination
yield product 3a and release Pd(0) catalyst. It should be
mentioned that a Pd−nitrene pathway cannot be ruled out
(pathway b).
1-(tert-Butyl)-2-phenyl-1H-benzo[d]imidazole
(3a):
White solid; Yield: 91% (22.7 mg); 1H NMR (600 MHz,
CDCl3) δ 7.82 – 7.77 (m, 1H), 7.75 – 7.71 (m, 1H), 7.49 (d,
J = 6.9 Hz, 2H), 7.47 – 7.40 (m, 3H), 7.29 – 7.27 (m, 2H),
1.63 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 153.5, 143.2,
135.8, 134.9, 129.7, 129.0, 127.8, 122.0, 121.9, 120.2,
114.7, 58.9, 31.4. HRMS (ESI-TOF) m/z: calculated for
C17H18N2Na+: 273.1362 (M + Na)+, found: 273.1370.
1-(tert-Butyl)-6-methyl-2-phenyl-1H-benzo[d]imidazole
1
(3b): White solid; Yield: 91% (24.1 mg); H NMR (600
MHz, CDCl3) δ 7.65 (d, J = 8.1 Hz, 1H), 7.51 (s, 1H), 7.47
(d, J = 6.8 Hz, 2H), 7.44 – 7.39 (m, 3H), 7.10 (d, J = 8.1
Hz, 1H), 2.54 (s, 3H), 1.61 (s, 9H). 13C NMR (151 MHz,
CDCl3) δ 153.1, 141.4, 136.0, 135.1, 131.6, 129.7, 128.9,
127.7, 123.4, 119.6, 114.6, 58.7, 31.4, 22.2. HRMS (ESI-
TOF) m/z: calculated for C18H20N2Na+: 287.1519 (M +
Na)+, found: 287.1525.
1-(tert-Butyl)-6-methoxy-2-phenyl-1H-
benzo[d]imidazole (3c): White solid; Yield: 90% (25.2
1
mg); H NMR (600 MHz, CDCl3) δ 7.66 (d, J = 8.7 Hz,
1H), 7.53 – 7.34 (m, 5H), 7.20 (s, 1H), 6.94 (d, J = 8.1 Hz,
1H), 3.91 (s, 3H), 1.60 (s, 9H). 13C NMR (151 MHz,
CDCl3) δ 155.5, 153.0, 138.0, 135.9, 135.4, 129.7, 128.9,
127.7, 120.3, 110.1, 99.6, 58.7, 56.1, 31.3. HRMS (ESI-
TOF) m/z: calculated for C18H20N2NaO+:303.1468 (M +
Na)+, found: 303.1474.
Scheme 5. Proposed Mechanism.
4
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10.1002/adsc.201801367
Advanced Synthesis & Catalysis
1-(tert-Butyl)-6-fluoro-2-phenyl-1H-benzo[d]imidazole
(3d): White solid; Yield: 93% (24.9 mg); H NMR (600
mg); 1H NMR (600 MHz, CDCl3) δ 7.47 (d, J = 6.7 Hz,
2H), 7.45 – 7.38 (m, 3H), 7.35 (s, 1H), 6.93 (s, 1H), 2.64 (s,
3H), 2.50 (s, 3H), 1.59 (s, 9H). 13C NMR (151 MHz,
CDCl3) δ 152.2, 140.6, 136.2, 134.7, 131.4, 129.9, 129.3,
128.8, 127.7, 123.8, 112.2, 58.6, 31.4, 22.1, 16.9. HRMS
1
MHz, CDCl3) δ 7.68 (dd, J = 8.8, 5.4 Hz, 1H), 7.47 (d, J =
6.7 Hz, 2H), 7.45 – 7.39 (m, 4H), 7.03 (td, J = 9.1, 2.2 Hz,
1H), 1.59 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 158.7 (d,
J = 236.8 Hz), 154.2 (d, J = 2.9 Hz), 139.6, 135.5, 134.7 (d, (ESI-TOF) m/z: calculated for C19H22N2Na+: 301.1675 (M
J = 12.9 Hz), 129.6, 129.1, 127.8, 120.6 (d, J = 10.3 Hz),
110.2 (d, J = 24.9 Hz), 101.3 (d, J = 28.7 Hz), 59.1, 31.3.
HRMS (ESI-TOF) m/z: calculated for C17H17FN2Na+:
291.1268 (M + Na)+, found: 291.1276.
+ Na)+, found: 301.1680.
1-(tert-Butyl)-2-(p-tolyl)-1H-benzo[d]imidazole
(3k):
1
White solid; Yield: 94% (24.8 mg); H NMR (600 MHz,
CDCl3) δ 7.78 (dd, J = 8.5, 4.3 Hz, 1H), 7.71 (dd, J = 8.5,
4.3 Hz, 1H), 7.36 (d, J = 7.9 Hz, 2H), 7.28 – 7.25 (m, 2H),
1-(tert-Butyl)-6-chloro-2-phenyl-1H-benzo[d]imidazole
1
(3e): White solid; Yield: 76% (21.6 mg); H NMR (600
7.22 (d, J = 7.9 Hz, 2H), 2.42 (s, 3H), 1.62 (s, 9H). 13
C
MHz, CDCl3) δ 7.73 (s, 1H), 7.69 (d, J = 8.5 Hz, 1H), 7.49
– 7.47 (m, 3H), 7.46 – 7.42 (m, 2H), 7.29 – 7.27 (m, 1H),
1.62 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 154.4, 141.8,
135.4, 135.3, 129.6, 129.2, 127.9, 127.6, 122.5, 120.8,
114.5, 59.3, 31.4. HRMS (ESI-TOF) m/z: calculated for
C17H17ClN2Na+: 307.0972 (M + Na)+, found: 307.0982.
NMR (151 MHz, CDCl3) δ 153.8, 143.3, 138.8, 134.9,
132.8, 129.5, 128.4, 121.8, 121.7, 120.1, 114.6, 58.8, 31.4,
21.4. HRMS (ESI-TOF) m/z: calculated for C18H20N2Na+:
287.1519 (M + Na)+, found: 287.1521.
1-(tert-Butyl)-2-(4-methoxyphenyl)-1H-
benzo[d]imidazole (3l): White solid; Yield: 83% (23.2
1
1-(tert-Butyl)-2-phenyl-6-(trifluoromethyl)-1H-
benzo[d]imidazole (3f): White solid; Yield: 55% (17.5
mg); 1H NMR (600 MHz, CDCl3) δ 7.99 (s, 1H), 7.84 (d, J
= 8.4 Hz, 1H), 7.53 (d, J = 8.4 Hz, 1H), 7.49 – 7.42 (m,
5H), 1.64 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 156.1,
145.4, 135.1, 134.3, 129.5, 129.4, 127.9, 124.9 (q, J =
270.9 Hz), 124.1 (q, J = 32.1 Hz), 120.5, 118.9 (q, J = 3.5
Hz), 112.1 (q, J = 4.4 Hz), 59.6, 31.5. HRMS (ESI-TOF)
m/z: calculated for C18H17F3N2Na+: 341.1236 (M + Na)+,
found: 341.1244.
mg); H NMR (600 MHz, CDCl3) δ 7.80 – 7.74 (m, 1H),
7.74 – 7.69 (m, 1H), 7.39 (d, J = 8.6 Hz, 2H), 7.28 – 7.25
(m, 2H), 6.94 (d, J = 8.6 Hz, 2H), 3.86 (s, 3H), 1.62 (s, 9H).
13C NMR (151 MHz, CDCl3) δ 160.1, 153.5, 143.2, 134.9,
130.9, 127.9, 121.8, 121.7, 120.1, 114.6, 113.2, 58.9, 55.3,
31.4.
HRMS
(ESI-TOF)
m/z:
calculated
for
C18H20N2NaO+:303.1468 (M + Na)+, found: 303.1472.
2-([1,1'-Biphenyl]-4-yl)-1-(tert-butyl)-1H-
benzo[d]imidazole (3m): White solid; Yield: 95% (30.9
mg); 1H NMR (600 MHz, CDCl3) δ 7.83 – 7.78 (m, 1H),
7.77 – 7.72 (m, 1H), 7.66 (dd, J = 8.0, 1.7 Hz, 4H), 7.56 (d,
J = 8.0 Hz, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.39 (t, J = 7.4
Hz, 1H), 7.31 – 7.27 (m, 2H), 1.67 (s, 9H). 13C NMR (151
MHz, CDCl3) δ 153.3, 143.3, 141.7, 140.3, 135.0, 134.7,
130.1, 128.8, 127.6, 127.1, 126.4, 122.0, 121.8, 120.2,
114.7, 58.9, 31.5. HRMS (ESI-TOF) m/z: calculated for
C23H22N2Na+: 349.1675 (M + Na)+, found: 349.1676.
Methyl 1-(tert-Butyl)-2-phenyl-1H-benzo[d]imidazole-
6-carboxylate (3g): White solid; Yield: 43% (13.2 mg);
1H NMR (600 MHz, CDCl3) δ 8.49 (s, 1H), 7.99 (d, J = 8.4
Hz, 1H), 7.77 (d, J = 8.4 Hz, 1H), 7.50 – 7.42 (m, 5H),
3.97 (s, 3H), 1.65 (s, 9H). 13C NMR (151 MHz, CDCl3) δ
167.7, 156.3, 146.8, 135.2, 134.6, 129.5, 129.3, 127.9,
123.7, 123.3, 119.7, 117.0, 59.6, 52.2, 31.6. HRMS (ESI-
+
TOF) m/z: calculated for C19H20N2NaO2 : 331.1417 (M +
Na)+, found: 331.1422.
1-(tert-Butyl)-2-(4-fluorophenyl)-1H-benzo[d]imidazole
(3n): White solid; Yield: 82% (22.1 mg); 1H NMR (600
MHz, CDCl3) δ 7.80 – 7.75 (m, 1H), 7.75 – 7.70 (m, 1H),
7.46 (dd, J = 8.5, 5.4 Hz, 2H), 7.30 – 7.27 (m, 2H), 7.12 (t,
J = 8.6 Hz, 2H), 1.62 (s, 9H). 13C NMR (151 MHz, CDCl3)
δ 163.1 (d, J = 248.7 Hz), 152.4, 143.2, 134.9, 131.9 (d, J
= 3.6 Hz), 131.5 (d, J = 8.5 Hz), 122.1, 122.0, 120.2,
114.9 (d, J = 22.1 Hz), 114.7, 59.0, 31.5. HRMS (ESI-TOF)
m/z: calculated for C17H17FN2Na+: 291.1268 (M + Na)+,
found: 291.1279.
1-(tert-Butyl)-2-phenyl-1H-benzo[d]imidazole-6-
carbonitrile (3h): White solid; Yield: 43% (11.8 mg); H
1
NMR (600 MHz, CDCl3) δ 8.07 (s, 1H), 7.82 (d, J = 8.3
Hz, 1H), 7.54 (d, J = 8.3 Hz, 1H), 7.52 – 7.41 (m, 5H),
1.63 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 157.0, 146.1,
134.6, 134.4, 129.6, 129.4, 128.0, 125.3, 121.1, 120.2,
119.4, 104.9, 59.9, 31.5. HRMS (ESI-TOF) m/z: calculated
for C18H17N3Na+: 298.1315 (M + Na)+, found: 298.1320.
1-(tert-Butyl)-5-methyl-2-phenyl-1H-benzo[d]imidazole
(3i): White solid; Yield: 87% (22.9 mg); H NMR (600
1-(tert-Butyl)-2-(4-chlorophenyl)-1H-benzo[d]imidazole
(3o): White solid; Yield: 76% (21.7 mg); 1H NMR (600
MHz, CDCl3) δ 7.77 (dd, J = 6.1, 3.2 Hz, 1H), 7.72 (dd, J
= 6.1, 3.2 Hz, 1H), 7.45 – 7.39 (m, 4H), 7.28 (dd, J = 6.1,
3.2 Hz, 2H), 1.62 (s, 9H). 13C NMR (151 MHz, CDCl3) δ
152.2, 143.2, 135.2, 134.9, 134.3, 131.0, 128.1, 122.2,
122.0, 120.2, 114.7, 59.0, 31.5. HRMS (ESI-TOF) m/z:
calculated for C17H17ClN2Na+: 307.0972 (M + Na)+, found:
307.0985.
1
MHz, CDCl3) δ 7.60 (d, J = 8.5 Hz, 1H), 7.56 (s, 1H), 7.47
(d, J = 6.7 Hz, 2H), 7.45 – 7.39 (m, 3H), 7.10 (d, J = 8.5
Hz, 1H), 2.48 (s, 3H), 1.60 (s, 9H). 13C NMR (151 MHz,
CDCl3) δ 153.5, 143.6, 135.9, 132.9, 131.5, 129.7, 128.9,
127.7, 123.4, 119.8, 114.1, 58.7, 31.4, 21.2. HRMS (ESI-
TOF) m/z: calculated for C18H20N2Na+: 287.1519 (M +
Na)+, found: 287.1529.
1-(tert-Butyl)-4,6-dimethyl-2-phenyl-1H-
1-(tert-Butyl)-2-(4-(trifluoromethyl)phenyl)-1H-
benzo[d]imidazole (3j): White solid; Yield: 91% (25.3
benzo[d]imidazole (3p): White solid; Yield: 89% (28.3
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801367
Advanced Synthesis & Catalysis
1
mg); H NMR (600 MHz, CDCl3) δ 7.79 (dd, J = 6.3, 2.9
J = 7.5 Hz, 1H), 7.31 (d, J = 7.2 Hz, 1H), 7.30 – 7.27 (m,
Hz, 1H), 7.74 (dd, J = 6.3, 2.9 Hz, 1H), 7.70 (d, J = 8.0 Hz,
2H), 7.63 (d, J = 8.0 Hz, 2H), 7.33 – 7.28 (m, 2H), 1.63 (s,
9H). 13C NMR (151 MHz, CDCl3) δ 151.8, 143.2, 139.6,
134.9, 131.2 (q, J = 34.2 Hz), 130.2, 124.8 (q, J = 3.8 Hz),
123.0, 122.5, 122.2, 120.3, 114.7, 59.1, 31.8. HRMS (ESI-
TOF) m/z: calculated for C18H17F3N2Na+: 341.1236 (M +
Na)+, found: 341.1242.
2H), 7.25 – 7.21 (m, 2H), 2.18 (s, 3H), 1.59 (s, 9H). 13
C
NMR (151 MHz, CDCl3) δ 152.5, 143.6, 137.2, 135.6,
134.4, 129.9, 129.7, 129.1, 125.1, 121.8, 121.6, 120.1,
114.5, 58.7, 30.7, 19.9. HRMS (ESI-TOF) m/z: calculated
for C18H20N2Na+: 287.1519 (M + Na)+, found: 287.1509.
1-(tert-Butyl)-2-(2-fluorophenyl)-1H-benzo[d]imidazole
(3w): White solid; Yield: 93% (24.9 mg); 1H NMR (600
MHz, CDCl3) δ 7.83 – 7.77 (m, 1H), 7.76 – 7.72 (m, 1H),
7.49 (td, J = 7.4, 1.4 Hz, 1H), 7.47 – 7.43 (m, 1H), 7.31 –
7.27 (m, 2H), 7.23 (t, J = 7.5 Hz, 1H), 7.13 (t, J = 8.9 Hz,
Methyl
4-(1-(tert-butyl)-1H-benzo[d]imidazol-2-
1
yl)benzoate (3q): White solid; Yield: 93% (28.6 mg); H
NMR (600 MHz, CDCl3) δ 8.11 (d, J = 8.2 Hz, 2H), 7.81 –
7.76 (m, 1H), 7.76 – 7.71 (m, 1H), 7.58 (d, J = 8.2 Hz, 2H), 1H), 1.65 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 160.4 (d,
7.31 – 7.27 (m, 2H), 3.96 (s, 3H), 1.62 (s, 9H). 13C NMR
(151 MHz, CDCl3) δ 166.6, 152.3, 143.3, 140.5, 134.9,
130.6, 129.8, 129.0, 122.3, 122.1, 120.3, 114.7, 59.0, 52.3,
J = 247.1 Hz), 147.3, 143.6, 134.8, 131.5 (d, J = 2.4 Hz),
131.3 (d, J = 8.0 Hz), 124.2 (d, J = 16.2 Hz), 123.9 (d, J =
3.5 Hz), 122.2, 121.8, 120.3, 115.4 (d, J = 20.2 Hz), 114.6,
58.9, 30.5. HRMS (ESI-TOF) m/z: calculated for
C17H17FN2Na+: 291.1268 (M + Na)+, found: 291.1275.
31.5.
HRMS
(ESI-TOF)
m/z:
calculated
for
C19H20N2NaO2 : 331.1417 (M + Na)+, found: 331.1428.
+
4-(1-(tert-Butyl)-1H-benzo[d]imidazol-2-yl)benzonitrile
(3r): Wite solid; Yield: 91% (25.0 mg,); H NMR (600
1-(tert-Butyl)-2-(3,4-dimethylphenyl)-1H-
1
benzo[d]imidazole (3x): White solid; Yield: 94% (26.1
mg); 1H NMR (600 MHz, CDCl3) δ 7.79 – 7.74 (m, 1H),
7.73 – 7.69 (m, 1H), 7.28 – 7.23 (m, 3H), 7.17 (q, J = 8.6
Hz, 2H), 2.32 (s, 3H), 2.30 (s, 3H), 1.63 (s, 9H). 13C NMR
(151 MHz, CDCl3) δ 153.9, 143.2, 137.4, 136.0, 134.9,
133.1, 130.6, 128.8, 127.1, 121.74, 121.67, 120.1, 114.6,
58.8, 31.4, 19.69, 19.67. HRMS (ESI-TOF) m/z: calculated
for C19H22N2Na+: 301.1675 (M + Na)+, found: 301.1678.
MHz, CDCl3) δ 7.80 – 7.76 (m, 1H), 7.74 (d, J = 8.3 Hz,
3H), 7.63 (d, J = 8.2 Hz, 2H), 7.34 – 7.28 (m, 2H), 1.63 (s,
9H). 13C NMR (151 MHz, CDCl3) δ 151.2, 143.3, 140.7,
134.9, 131.6, 130.5, 122.7, 122.3, 120.4, 118.3, 114.8,
113.0, 59.1, 31.6. HRMS (ESI-TOF) m/z: calculated for
C18H17N3Na+: 298.1315 (M + Na)+, found: 298.1322.
1-(tert-Butyl)-2-(m-tolyl)-1H-benzo[d]imidazole
(3s):
White solid; Yield: 96% (25.4 mg); 1H NMR (600 MHz,
CDCl3) δ 7.79 – 7.76 (m, 1H), 7.74 – 7.70 (m, 1H), 7.33 –
7.25 (m, 6H), 2.40 (s, 3H), 1.63 (s, 9H). 13C NMR (151
MHz, CDCl3) δ 153.8, 143.3, 137.5, 135.7, 134.8, 130.2,
129.6, 127.5, 126.8, 121.8, 121.7, 120.1, 114.6, 58.8, 31.4,
21.3. HRMS (ESI-TOF) m/z: calculated for C18H20N2Na+:
287.1519 (M + Na)+, found: 287.1511.
1-(tert-Butyl)-2-(naphthalen-2-yl)-1H-
benzo[d]imidazole (3y): White solid; Yield: 96% (28.8
mg); 1H NMR (600 MHz, CDCl3) δ 8.01 (s, 1H), 7.92 –
7.87 (m, 3H), 7.84 – 7.80 (m, 1H), 7.78 – 7.74 (m, 1H),
7.59 – 7.52 (m, 3H), 7.33 – 7.28 (m, 2H), 1.65 (s, 9H). 13C
NMR (151 MHz, CDCl3) δ 153.5, 143.4, 135.0, 133.2,
132.5, 129.1, 128.2, 127.8, 127.3, 127.2, 126.8, 126.6,
122.0, 121.9, 120.2, 114.7, 58.9, 31.5. HRMS (ESI-TOF)
m/z: calculated for C21H20N2Na+: 323.1519 (M + Na)+,
found: 323.1528.
1-(tert-Butyl)-2-(3-methoxyphenyl)-1H-
benzo[d]imidazole (3t): White solid; Yield: 81% (22.7
1
mg); H NMR (600 MHz, CDCl3) δ 7.80 – 7.77 (m, 1H),
7.74 – 7.71 (m, 1H), 7.32 (t, J = 7.9 Hz, 1H), 7.29 – 7.25
(m, 2H), 7.06 (d, J = 7.5 Hz, 1H), 7.04 (s, 1H), 7.00 (dd, J
= 8.3, 2.0 Hz, 1H), 3.84 (s, 3H), 1.64 (s, 9H). 13C NMR
(151 MHz, CDCl3) δ 158.9, 153.3, 143.2, 137.0, 134.8,
1-(tert-Butyl)-2-(furan-2-yl)-1H-benzo[d]imidazole (3z):
White solid; Yield: 94% (22.6 mg); H NMR (600 MHz,
CDCl3) δ 7.83 – 7.78 (m, 1H), 7.77 – 7.71 (m, 1H), 7.55 (s,
1
128.8, 122.4, 122.0, 121.8, 120.2, 115.1, 114.9, 114.6, 58.9, 1H), 7.30 – 7.27 (m, 2H), 6.76 (d, J = 3.1 Hz, 1H), 6.55 –
55.3, 31.3. HRMS (ESI-TOF) m/z: calculated for
6.53 (m, 1H), 1.68 (s, 9H). 13C NMR (151 MHz, CDCl3) δ
146.0, 143.6, 143.0, 142.5, 135.1, 122.8, 122.0, 120.7,
114.6, 112.6, 111.4, 59.2, 30.2. HRMS (ESI-TOF) m/z:
calculated for C15H16N2NaO+: 263.1155 (M + Na)+, found:
263.1159.
C18H20N2NaO+:303.1468 (M + Na)+, found: 303.1462.
1-(tert-Butyl)-2-(3-fluorophenyl)-1H-benzo[d]imidazole
(3u): White solid; Yield: 94% (25.1 mg); 1H NMR (600
MHz, CDCl3) δ 7.80 – 7.77 (m, 1H), 7.74 – 7.71 (m, 1H),
7.40 (dd, J = 13.8, 7.8 Hz, 1H), 7.32 – 7.27 (m, 3H), 7.22
(d, J = 8.9 Hz, 1H), 7.17 (td, J = 8.5, 1.9 Hz, 1H), 1.64 (s,
9H). 13C NMR (151 MHz, CDCl3) δ 161.9 (d, J = 248.3
Hz), 151.9 (d, J = 2.4 Hz), 143.2, 137.8 (d, J = 8.1 Hz),
134.8, 129.4 (d, J = 8.3 Hz), 125.7 (d, J = 3.1 Hz), 122.3,
122.0, 120.3, 117.0 (d, J = 22.1 Hz), 116.1 (d, J = 20. 6
Hz), 114.7, 59.0, 31.4. HRMS (ESI-TOF) m/z: calculated
for C17H17FN2Na+: 291.1268 (M + Na)+, found: 291.1265.
1-(tert-Butyl)-2-(thiophen-2-yl)-1H-benzo[d]imidazole
1
(3aa): White solid; Yield: 93% (23.8 mg); H NMR (600
MHz, CDCl3) δ 7.82 – 7.76 (m, 1H), 7.76 – 7.70 (m, 1H),
7.47 (dd, J = 5.1, 0.9 Hz, 1H), 7.29 – 7.27 (m, 2H), 7.25
(dd, J = 3.5, 0.9 Hz, 1H), 7.08 (dd, J = 5.1, 3.5 Hz, 1H),
1.70 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 146.5, 143.1,
135.2, 135.1, 130.3, 127.3, 126.3, 122.4, 122.0, 120.4,
114.7, 59.4, 31.0. HRMS (ESI-TOF) m/z: calculated for
C15H16N2NaS+: 279.0926 (M + Na)+, found: 279.0936.
1-(tert-Butyl)-2-(o-tolyl)-1H-benzo[d]imidazole
(3v):
White solid; Yield: 98% (25.8 mg); 1H NMR (600 MHz,
1-(tert-Butyl)-2-(pyridin-4-yl)-1H-benzo[d]imidazole
1
CDCl3) δ 7.81 – 7.77 (m, 1H), 7.76 – 7.71 (m, 1H), 7.34 (t,
(3ab): White solid; Yield: 71% (17.8 mg); H NMR (600
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801367
Advanced Synthesis & Catalysis
MHz, CDCl3) δ 8.71 (d, J = 4.2 Hz, 2H), 7.78 (dd, J = 5.3,
3.9 Hz, 1H), 7.74 (dd, J = 5.3, 3.9 Hz, 1H), 7.45 (d, J = 5.7
Hz, 2H), 7.34 – 7.28 (m, 2H), 1.65 (s, 9H). 13C NMR (151
MHz, CDCl3) δ 150.5, 149.3, 144.2, 143.3, 134.9, 124.5,
122.6, 122.3, 120.4, 114.8, 59.1, 31.5. HRMS (ESI-TOF)
m/z: calculated for C16H17N3Na+: 274.1315 (M + Na)+,
found: 274.1314.
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Acknowledgements
The work was supported by the National Natural Science
Founda-tion of China (No.216721626 and No.2137217) and
Shanghai Science and Technology Commission (14DZ2261100).
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Advanced Synthesis & Catalysis
FULL PAPER
Synthesis of Benzimidazoles through Palladium-
Catalyzed Amination of 2-Iodobenzimines with
Diaziridinone
Adv. Synth. Catal. Year, Volume, Page – Page
Ding Ma, Xiaoming Ji, Zhuo Wu, Cang Cheng, Bo
Zhou, Yanghui Zhang *
9
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