Palladium-Catalyzed Ligand-Free C-N Coupling Reactions: Selective Diheteroarylation of Amines with 2-Halobenzimidazoles

Article abstract of DOI:10.1002/asia.201901465

2-Aminobenzimidazoles are widely present in a number of bioactive molecules. Generally, the preparation of these molecules could be realized by the mono-substitution of 2-halobenzimidazoles with amines. However, rare examples were reported for the di-subs

Full text of DOI:10.1002/asia.201901465

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Palladium-Catalyzed Ligand-Free C-N Coupling Reactions:
Selective Diheteroarylation of Amines with 2-Halobenzimidazoles
Authors: Francis Verpoort, Wei Sang, Ayao Jean Gavi, Bao-Yi Yu,
Hua Cheng, Ye Yuan, Yuan Wu, Petra Lommens, and Cheng
Chen
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To be cited as: Chem. Asian J. 10.1002/asia.201901465
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A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

10.1002/asia.201901465
Chemistry - An Asian Journal
Supporting Information for
Palladium-Catalyzed
Ligand-Free
C-N
Coupling
Reactions:
Selective
Diheteroarylation of Amines with 2-Halobenzimidazoles
Wei Sang,[a, b] Ayao Jean Gavi,[c] Bao-Yi Yu,[d] Hua Cheng,[e] Ye Yuan,[a] Yuan Wu,[f]
Petra Lommens,[c] Cheng Chen*[a] and Francis Verpoort*[a, g, h]
[a]
State Key Laboratory of Advanced Technology for Materials Synthesis and
Processing, Wuhan University of Technology, 122 Luoshi Road, Wuhan 430070, P. R.
China;
[b] School of Materials Science and Engineering, Wuhan University of Technology,
122 Luoshi Road, Wuhan 430070, P. R. China;
[c] Odisee/KU Leuven Technology Campus, Gebroeders de Smetstraat 1, 9000 Ghent,
Belgium;
[d]
Key Laboratory of Urban Agriculture (North China), Ministry of Agriculture,
Beijing University of Agriculture, Beinong Road 7, Beijing 102206, P. R. China;
[e]
Department of Chemical Engineering and Food Science, Hubei University of Arts
and Science, Xiangyang 441053, P. R. China;
[f]
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College
of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, P.
R. China;
[g] National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050,
Russian Federation.
[h] Ghent University Global Campus, 119 Songdomunhwa-Ro, Yeonsu-Gu, Incheon
21985, Korea.
Contents:
1. Catalyst Poisoning by the mercury test.................................................................... S2-S3
2. Characterization data for compounds 1t, 3a, 4a-4t, 5a and 7a-7j......................... S4-S14
3. Original 1H and 13C NMR spectra for 1t, 3a, 4a-4t, 5a and 7a-7j ...................... S15-S47
S1
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1. Catalyst Poisoning by the mercury test
To gain more information about the nature of the active catalyst, we carried out
catalyst poisoning experiments by the mercury test (as listed in Table S1). It was
noted that without metallic mercury, 4a was obtained in 86% yield (entry 1). In
contrast, reversed selectivity of 3a and 4a (70% of 3a and 11% of 4a) was detected if
100 equiv. of mercury vs. PdCl2 was added simultaneously with all other reagents
(entry 2). Further increasing the mercury loadings led to reduced yields of both 3a and
4a, with 3a remaining as the major product (entries 3-4). It was suggested by some
authors that mercury should be added after the catalyst was activated,[1] so a separate
experiment in which mercury was added after all other reagents were refluxed for 10
min (entry 5). The result indicated that increased yields of both 3a (70%) and 4a (14%)
were obtained (entry 5 vs. entry 4). It was noted that only the mercury test was not
sufficient to distinguish truly homogeneous molecular catalysis from nanoparticle
metal catalysis.[2] Nevertheless, it at least gave us the first clue to clearly spot that
metallic mercury had a considerable impact on the selectivity as well as the yields of
3a and 4a.
Table S1. Catalyst Poisoning by the mercury test[a]
Yield (%)[b]
Entry
x
3a
-
4a
86
11
10
8
5a
-
1
0
2
0.5 (100 equiv. vs. PdCl2)
1.5 (300 equiv. vs. PdCl2)
2.5 (500 equiv. vs. PdCl2)
2.5 (500 equiv. vs. PdCl2)
70
56
58
72
-
3
-
4
-
5[c]
14
-
[a] Conditions: 1a (0.2 mmol, 33.3 mg), 2a (0.1 mmol, 9 μL), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (130.4 mg, 0.4 mmol), Hg(0) (x
mmol) and toluene (0.5 mL) at reflux under argon for 16 h. [b] NMR yields using 1,3,5-trimethoxybenzene as an internal standard
(average of two consistent runs). [c] Hg (0) (x mmol) was added after the other components were refluxed for 10 min.
S2
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References
[1]
a) K. S. Weddle, J. D. Aiken, R. G. Finke, J. Am. Chem. Soc. 1998, 120, 5653-5666. b) R. H.
Crabtree, Chem. Rev. 2011, 112, 1536-1554; c) J. F. Sonnenberg, R. H. Morris, Catal. Sci.
Technol. 2014, 4, 3426-3438.
[2]
V. M. Chernyshev, A. V. Astakhov, I. E. Chikunov, R. V. Tyurin, D. B. Eremin, G. S. Ranny, V.
N. Khrustalev, V. P. Ananikov, ACS Catal. 2019, 9, 2984-2995.
S3
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2. Characterization data for compounds 1t, 3a, 4a-4t, 5a and 7a-7j
2,5,6-Trichloro-1-methyl-1H-benzo[d]imidazole (1t).
A
mixture
of
2,5,6-trichloro-1H-benzo[d]imidazole (199.3 mg, 0.90 mmol) and 60% NaH (38.0 mg,
0.99 mmol) in DMF (2.0 mL) gave pure product 1t (186.5 mg, 0.79 mmol) in 88%
yield. White powder: m.p. 212.0-213.4 ℃. 1H NMR (500 MHz, CDCl3) δ 7.79 (s, 1H),
7.43 (s, 1H), 3.78 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 142.9, 140.8, 134.7, 127.5,
127.1, 120.7, 110.8, 30.8. HR-MS (ESI positive): m/z calcd. for C8H6Cl3N2 [M+H]+:
234.95911; Found: 234.95913.
1-Methyl-N-phenyl-1H-benzo[d]imidazol-2-amine (3a). A mixture of 1a (0.2 mmol,
33.3 mg), 2a (0.2 mmol, 18 μL), Pd(OAc)2 (0.005 mmol, 1.1 mg), BINAP (0.005
mmol, 3.1 mg), NaH (60% dispersed in mineral oil, 0.2 mmol, 8.0 mg) and toluene
(0.5 mL) provided 3a (0.044 mmol, 9.8 mg) in 22% yield. White powder: m.p.
199.2-200.0 ℃. 1H NMR (500 MHz, CDCl3) δ 7.61 (d, J = 7.3 Hz, 1H), 7.46 (d, J =
7.9 Hz, 2H), 7.35 (dd, J = 8.5, 7.3 Hz, 2H), 7.26 – 7.16 (m, 3H), 7.05 (dd, J = 7.6, 7.4
Hz, 1H), 6.45 (s, 1H), 3.62 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 150.2, 141.6,
140.7, 134.5, 129.3, 122.4, 121.7, 120.8, 118.4, 117.5, 107.8, 29.2. HR-MS (ESI
positive): m/z calcd. for C14H14N3 [M+H]+: 224.11822; Found: 224.11818.
1-Methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-N-phenyl-1H-benzo[d]imidazol-
2-amine (4a). A mixture of 1a (0.2 mmol, 33.3 mg), 2a (0.1 mmol, 9 μL), PdCl2
(0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided
4a (0.083 mmol, 29.3 mg) in 83% yield. White powder: m.p. 226.3-227.6 ℃. 1H NMR
(500 MHz, CDCl3) δ 7.69 (d, J = 7.2 Hz, 2H), 7.34 (dd, J = 8.2, 8.0 Hz, 2H), 7.32 –
7.22 (m, 6H), 7.15 (dd, J = 7.6, 7.4 Hz, 1H), 6.95 (d, J = 7.6 Hz, 2H), 3.53 (s, 6H).
13C NMR (126 MHz, CDCl3) δ 149.3, 143.5, 141.3, 135.1, 129.9, 124.5, 122.7, 122.4,
120.4, 119.7, 109.3, 30.3. HR-MS (ESI): m/z calcd. for C22H20N5 [M+H]+: 354.17132;
Found: 354.17112.
1-Methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-N-(p-tolyl)-1H-benzo[d]imidazol
-2-amine (4b). A mixture of 1a (0.2 mmol, 33.3 mg), 2b (0.1 mmol, 11 μL), PdCl2
(0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided
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1
4b (0.087 mmol, 32.0 mg) in 87% yield. White powder: m.p. 174.1-175.6 ℃. H
NMR (500 MHz, CDCl3) δ 7.70 – 7.65 (m, 2H), 7.31 – 7.27 (m, 4H), 7.25 – 7.20 (m,
2H), 7.15 (d, J = 8.1 Hz, 2H), 6.89 (d, J = 8.4 Hz, 2H), 3.49 (s, 6H), 2.33 (s, 3H). 13C
NMR (126 MHz, CDCl3) δ 149.8, 141.3, 140.9, 135.1, 134.6, 130.5, 122.5, 122.3,
121.2, 119.6, 109.1, 30.3, 20.8. HR-MS (ESI): m/z calcd. for C23H22N5 [M+H]+:
368.18697; Found: 368.18683.
N-(4-Methoxyphenyl)-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[
d]imidazol-2-amine (4c). A mixture of 1a (0.2 mmol, 33.3 mg), 2c (0.1 mmol, 12.3
mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 4c (0.084 mmol, 32.2 mg) in 84% yield. White powder: m.p. 201.7-202.0 ℃.
1H NMR (500 MHz, CDCl3) δ 7.67 (d, J = 6.8 Hz, 2H), 7.21 – 7.14 (m, 6H), 7.02 (d,
13
J = 9.0 Hz, 2H), 6.90 (d, J = 9.0 Hz, 2H), 3.80 (s, 3H), 3.45 (s, 6H). C NMR (126
MHz, CDCl3) δ 156.2, 149.3, 140.2, 135.2, 134.1, 122.9, 121.3, 121.2, 118.5, 114.2,
108.0, 54.5, 29.2. HR-MS (ESI): m/z calcd. for C23H22N5O [M+H]+: 384.18189;
Found: 384.18197.
N-(4-Isopropylphenyl)-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-benzo
[d]imidazol-2-amine (4d). A mixture of 1a (0.2 mmol, 33.3 mg), 2d (0.1 mmol, 14
μL), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 4d (0.09 mmol, 35.6 mg) in 90% yield. White powder: m.p. 199.0-199.8 ℃.
1H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 7.0 Hz, 2H), 7.31 – 7.25 (m, 6H), 7.22 (d, J
= 8.5 Hz, 2H), 6.95 (d, J = 8.5 Hz, 2H), 3.50 (s, 6H), 2.92 (h, J = 6.8 Hz, 1H), 1.27 (d, J
= 6.9 Hz, 6H). 13C NMR (126 MHz, CDCl3) δ 149.8, 145.5, 141.2, 141.0, 135.1, 127.9,
122.5, 122.3, 121.3, 119.6, 109.1, 33.5, 30.3, 24.0. HR-MS (ESI): m/z calcd. for
C25H26N5 [M+H]+: 396.21827; Found: 396.21836.
N-(4-(Tert-butyl)phenyl)-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-ben
zo[d]imidazol-2-amine (4e). A mixture of 1a (0.2 mmol, 33.3 mg), 2e (0.1 mmol, 16
μL), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 4e (0.089 mmol, 36.4 mg) in 89% yield. White powder: m.p. 228.0-229.4 ℃.
1H NMR (500 MHz, CDCl3) δ 7.68 (d, J = 7.5 Hz, 2H), 7.34 (d, J = 8.3 Hz, 2H), 7.29
– 7.23 (m, 6H), 6.92 (d, J = 8.3 Hz, 2H), 3.48 (s, 6H), 1.30 (s, 9H). 13C NMR (126
S5
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MHz, CDCl3) δ 149.7, 147.7, 141.2, 140.6, 135.1, 126.8, 122.5, 122.3, 120.8, 119.6,
109.1, 31.3, 30.3, 29.7. HR-MS (ESI): m/z calcd. for C26H28N5 [M+H]+: 410.23392;
Found: 410.23376.
N-(4-Iodophenyl)-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[d]i
midazol-2-amine (4f). A mixture of 1a (0.2 mmol, 33.3 mg), 2f (0.1 mmol, 21.9 mg),
PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 4f (0.088 mmol, 42.2 mg) in 88% yield. White powder: m.p. 209.5-211.0℃.
1
Isolated yield: 88%. H NMR (500 MHz, CDCl3) δ 7.69 (d, J = 7.6 Hz, 2H), 7.63 (d, J
= 8.8 Hz, 2H), 7.35 – 7.26 (m, 6H), 6.71 (d, J = 8.8 Hz, 2H), 3.55 (s, 6H). 13C NMR
(126 MHz, CDCl3) δ 147.6, 142.4, 140.1, 137.8, 134.0, 121.9, 121.5, 121.1, 118.8,
108.3, 87.0, 29.3. HR-MS (ESI): m/z calcd. for C22H19IN5 [M+H]+: 480.06797; Found:
480.06800.
N-(4-Bromophenyl)-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[d]
imidazol-2-amine (4g). A mixture of 1a (0.2 mmol, 33.3 mg), 2g (0.1 mmol, 17.2 mg),
PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 4g (0.09 mmol, 38.9 mg) in 90% yield. White powder: m.p. 215.7-216.2 ℃.
1H NMR (500 MHz, CDCl3) δ 7.62 (d, J = 7.5 Hz, 2H), 7.38 (d, J = 8.8 Hz, 2H), 7.27 –
7.19 (m, 6H), 6.77 (d, J = 8.9 Hz, 2H), 3.47 (s, 6H). 13C NMR (126 MHz, CDCl3) δ
147.7, 141.6, 140.1, 134.0, 131.9, 121.9, 121.5, 121.0, 118.7, 116.5, 108.3, 29.3.
HR-MS (ESI): m/z calcd. for C22H19BrN5 [M+H]+: 432.08183; Found: 432.08205.
N-(4-Chlorophenyl)-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[d
]imidazol-2-amine (4h). A mixture of 1a (0.2 mmol, 33.3 mg), 2h (0.1 mmol, 12.8
mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 4h (0.076 mmol, 29.5 mg) in 76% yield. White powder: m.p. 223.2-224.3 ℃.
1
Isolated yield: 76%. H NMR (500 MHz, CDCl3) δ 7.72 (d, J = 7.6 Hz, 2H), 7.35 –
7.28 (m, 8H), 6.96 – 6.90 (m, 2H), 3.56 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 148.9,
142.1, 141.1, 135.0, 130.0, 130.0, 122.9, 122.5, 121.8, 119.8, 109.3, 30.3. HR-MS
(ESI): m/z calcd. for C22H19ClN5 [M+H]+: 388.13235; Found: 388.13246.
N-(4-Fluorophenyl)-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[d]
imidazol-2-amine (4i). A mixture of 1a (0.2 mmol, 33.3 mg), 2i (0.1 mmol, 10 μL),
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PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 4i (0.078 mmol, 29.0 mg) in 78% yield. White powder: m.p. 201.0-202.4 ℃.
1H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 7.4 Hz, 2H), 7.35 – 7.26 (m, 6H), 7.14 – 7.00
(m, 4H), 3.52 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 159.9 (d, J = 245.3 Hz), 149.5,
141.1, 139.4 (d, J = 2.9 Hz), 135.0, 123.3 (d, J = 8.3 Hz), 122.7, 122.4, 119.6, 116.8 (d,
J = 22.9 Hz), 109.1, 30.2. HR-MS (ESI): m/z calcd. for C22H19FN5 [M+H]+:
372.16190; Found: 372.16171.
1-Methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-N-(4-(trifluoromethyl)phenyl)-1
H-benzo[d]imidazol-2-amine (4j). A mixture of 1a (0.2 mmol, 33.3 mg), 2j (0.1 mmol,
13 μL), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5
mL) provided 4j (0.072 mmol, 30.3 mg) in 72% yield. White powder: m.p.
210.3-211.7 ℃. 1H NMR (500 MHz, CDCl3) δ 7.72 (dd, J = 7.7, 1.3 Hz, 2H), 7.57 (d,
J = 8.5 Hz, 2H), 7.37 – 7.27 (m, 6H), 6.95 (d, J = 8.4 Hz, 2H), 3.62 (s, 6H). 13C NMR
(126 MHz, CDCl3) δ 147.9, 146.7, 141.1, 135.0, 127.2 (q, J = 3.9 Hz), 125.8 (q, J =
32.8 Hz), 124.0 (q, J = 288.0 Hz), 123.3, 122.8, 120.0, 118.7, 109.6, 30.3. HR-MS
+
(ESI): m/z calcd. for C23H19F3N5 [M+H]+: 422.15871; Found: 422.15859.
1-Methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-N-(m-tolyl)-1H-benzo[d]imidazo
l-2-amine (4k). A mixture of 1a (0.2 mmol, 33.3 mg), 2k (0.1 mmol, 11 μL), PdCl2
(0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided
4k (0.084 mmol, 30.8 mg) in 84% yield. White powder: m.p. 193.0-194.2 ℃. 1H NMR
(500 MHz, CDCl3) δ 7.72 – 7.66 (m, 2H), 7.33 – 7.26 (m, 5H), 7.25 – 7.20 (m, 2H),
13
6.96 (d, J = 7.6 Hz, 1H), 6.79 – 6.72 (m, 2H), 3.53 (s, 6H), 2.28 (s, 3H). C NMR
(126 MHz, CDCl3) δ 149.5, 143.4, 141.3, 140.1, 135.1, 129.7, 125.5, 122.6, 122.3,
121.1, 119.7, 117.7, 109.2, 30.3, 21.5. HR-MS (ESI): m/z calcd. for C23H22N5 [M+H]+:
368.18697; Found: 368.18678.
1-Methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-N-(o-tolyl)-1H-benzo[d]imidazol
-2-amine (4l). A mixture of 1a (0.2 mmol, 33.3 mg), 2l (0.1 mmol, 11 μL), PdCl2
(0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided
4l (0.085 mmol, 31.2 mg) in 85% yield. White powder: m.p. 244.6-245.3 ℃. 1H NMR
(500 MHz, CDCl3) δ 7.66 (d, J = 6.6 Hz, 2H), 7.33 – 7.27 (m, 1H), 7.27 – 7.19 (m,
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13
8H), 7.10 – 7.01 (m, 1H), 3.34 (s, 6H), 2.06 (s, 3H). C NMR (126 MHz, CDCl3) δ
150.5, 141.3, 141.3, 135.1, 133.3, 131.9, 127.7, 127.1, 125.3, 122.2, 122.2, 119.5,
108.8, 29.9, 18.1. HR-MS (ESI): m/z calcd. for C23H22N5 [M+H]+: 368.18697; Found:
368.18673.
N-Benzyl-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[d]imidazol-2
-amine (4m). A mixture of 1a (0.2 mmol, 33.3 mg), 2m (0.1 mmol, 11 μL), PdCl2
(0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided
1
4m (0.038 mmol, 14.0 mg) in 38% yield. White powder: m.p. 166.1-167.3℃. H
NMR (500 MHz, CDCl3) δ 7.68 (d, J = 7.5 Hz, 2H), 7.54 (d, J = 7.3 Hz, 2H), 7.26 –
7.20 (m, 7H), 7.16 (d, J = 7.0 Hz, 2H), 5.41 (s, 2H), 3.19 (s, 6H). 13C NMR (126 MHz,
CDCl3) δ 151.5, 141.3, 137.0, 134.9, 128.6, 128.5, 127.8, 122.3, 122.0, 118.9, 108.8,
57.0, 29.7. HR-MS (ESI): m/z calcd. for C23H22N5 [M+H]+: 368.18697; Found:
368.18687.
N-hexyl-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[d]imidazol-2-
amine (4n). A mixture of 1a (0.2 mmol, 33.3 mg), 2n (0.1 mmol, 13 μL), PdCl2
(0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided
1
4n (0.04 mmol, 14.5 mg) in 40% yield. White powder: m.p. 110.8-112.3℃. H NMR
(500 MHz, CDCl3) δ 7.74 – 7.68 (m, 2H), 7.30 – 7.20 (m, 6H), 4.20 – 4.10 (m, 2H),
3.33 (s, 6H), 1.93 (p, J = 7.7 Hz, 2H), 1.43 (q, J = 7.6 Hz, 2H), 1.36 – 1.30 (m, 4H),
0.88 (t, J = 6.9 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 151.6, 141.3, 134.9, 122.3,
121.9, 118.8, 108.8, 53.9, 31.6, 29.7, 28.8, 26.5, 22.6, 14.0. HR-MS (ESI): m/z calcd.
for C22H28N5 [M+H]+: 362.23392; Found: 362.23375.
1-Ethyl-N-(1-ethyl-1H-benzo[d]imidazol-2-yl)-N-phenyl-1H-benzo[d]imidazol-2-a
mine (4o). A mixture of 1o (0.2 mmol, 36.1 mg), 2a (0.1 mmol, 9 μL), PdCl2 (0.005
mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided 4o
1
(0.082 mmol, 31.3 mg) in 82% yield. White powder: m.p. 170.5-170.7 ℃. H NMR
(500 MHz, DMSO-d6) δ 7.54 (dd, J = 8.6, 8.4 Hz, 4H), 7.41 (dd, J = 8.0, 7.8 Hz, 2H),
7.30 – 7.17 (m, 5H), 7.01 (d, J = 7.9 Hz, 2H), 3.99 (q, J = 7.2 Hz, 4H), 1.07 (t, J = 7.2
Hz, 6H). 13C NMR (126 MHz, CDCl3) δ 148.6, 144.3, 141.4, 134.1, 129.7, 124.4,
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122.7, 122.3, 120.4, 119.9, 109.7, 39.0, 14.1. HR-MS (ESI positive): m/z calcd. for
C24H24N5 [M+H]+: 382.20262; Found: 382.20250.
1-Isobutyl-N-(1-isobutyl-1H-benzo[d]imidazol-2-yl)-N-phenyl-1H-benzo[d]imidazo
l-2-amine (4p). A mixture of 1p (0.2 mmol, 41.7 mg), 2a (0.1 mmol, 9 μL), PdCl2
(0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided
4p (0.085 mmol, 37.2 mg) in 85% yield. White powder: m.p. 74.3-75.6 ℃. 1H NMR
(500 MHz, CDCl3) δ 7.75 – 7.71 (m, 2H), 7.37 – 7.31 (m, 4H), 7.28 (d, J = 1.3 Hz,
3H), 7.27 – 7.25 (m, 1H), 7.20 – 7.15 (m, 1H), 7.08 – 7.03 (m, 2H), 3.67 (d, J = 7.7
Hz, 4H), 2.43 – 1.88 (m, 2H), 0.81 (d, J = 6.7 Hz, 12H). 13C NMR (126 MHz, CDCl3)
δ 149.3, 144.3, 141.2, 135.0, 129.7, 124.8, 122.5, 122.2, 121.5, 119.7, 110.1, 51.3,
28.5, 20.2. HR-MS (ESI positive): m/z calcd. for C28H32N5 [M+H]+: 438.26522;
Found: 438.26509.
1-Isopropyl-N-(1-isopropyl-1H-benzo[d]imidazol-2-yl)-N-phenyl-1H-benzo[d]imid
azol-2-amine (4q). A mixture of 1q (0.2 mmol, 38.9 mg), 2a (0.1 mmol, 9 μL),
Pd(OAc)2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.8 mg) and toluene (0.5 mL)
provided 4q (0.084 mmol, 34.4 mg) in 84% yield. White powder: m.p. 187.0-188.4 ℃.
1H NMR (500 MHz, CDCl3) δ 7.79 – 7.71 (m, 2H), 7.63 – 7.53 (m, 2H), 7.35 – 7.23
(m, 6H), 7.08 (dd, J = 7.6, 7.4 Hz, 1H), 6.83 (d, J = 7.6 Hz, 2H), 5.08 (h, J = 7.0 Hz,
13
2H), 1.52 (d, J = 7.0 Hz, 12H). C NMR (126 MHz, CDCl3) δ 147.7, 145.1, 142.0,
132.5, 129.5, 123.2, 122.5, 121.9, 120.3, 118.1, 112.1, 48.2, 20.8. HR-MS (ESI
positive): m/z calcd. for C26H28N5 [M+H]+: 410.23392; Found: 410.23471.
N,1-Diphenyl-N-(1-phenyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[d]imidazol-2-ami
ne (4r). A mixture of 1r (0.2 mmol, 45.7 mg), 2a (0.1 mmol, 9 μL), PdCl2 (0.005
mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided 4r
1
(0.082 mmol, 39.2 mg) in 82% yield. White powder: m.p. 231.5-232.9 ℃. H NMR
(500 MHz, CDCl3) δ 7.76 (d, J = 8.0 Hz, 2H), 7.29 – 7.17 (m, 14H), 7.09 (d, J = 8.0
Hz, 2H), 6.92 (dd, J = 7.8, 7.6 Hz, 2H), 6.83 (dd, J = 7.6, 7.4 Hz, 1H), 6.70 (d, J = 7.7
Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 150.0, 142.2, 141.3, 135.7, 135.1, 129.1,
128.7, 128.3, 127.4, 124.8, 123.3, 122.8, 122.6, 119.5, 109.8. HR-MS (ESI positive):
m/z calcd. for C32H24N5 [M+H]+: 478.20262; Found: 478.20189.
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1,5,6-Trimethyl-N-phenyl-N-(1,5,6-trimethyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[
d]imidazol-2-amine (4s). A mixture of 1s (0.2 mmol, 38.9 mg), 2a (0.1 mmol, 9 μL),
PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 4s (0.065 mmol, 26.6 mg) in 65% yield. White powder: m.p. 230.1-230.8 ℃.
1H NMR (500 MHz, CDCl3) δ 7.44 (s, 2H), 7.29 (dd, J = 8.6, 7.3 Hz, 2H), 7.12 – 7.04
(m, 3H), 6.85 (d, J = 7.5 Hz, 2H), 3.49 (s, 6H), 2.39 (s, 6H), 2.35 (s, 6H). 13C NMR
(126 MHz, CDCl3) δ 148.4, 144.0, 139.7, 133.5, 131.7, 131.0, 129.7, 123.8, 119.8,
119.5, 109.6, 30.2, 20.5, 20.2. HR-MS (ESI positive): m/z calcd. for C26H28N5
[M+H]+: 410.23392; Found: 410.23401.
5,6-Dichloro-N-(5,6-dichloro-1-methyl-1H-benzo[d]imidazol-2-yl)-1-methyl-N-phe
nyl-1H-benzo[d]imidazol-2-amine (4t). A mixture of 1t (0.2 mmol, 47.1 mg), 2a (0.1
mmol, 9 μL), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene
(0.5 mL) provided 4t (0.02 mmol, 9.8 mg) in 20% yield. White powder: m.p.
273.7-274.7℃. 1H NMR (500 MHz, CD2Cl2) δ 7.73 (s, 2H), 7.56 – 7.41 (m, 4H), 7.34
(dd, J = 7.8, 7.6 Hz, 1H), 7.08 (d, J = 7.8 Hz, 2H), 3.41 (s, 6H). 13C NMR (126 MHz,
CD2Cl2) δ 151.5, 142.4, 140.5, 134.6, 130.0, 126.2, 126.2, 126.1, 122.9, 120.4, 110.8,
30.5. HR-MS (ESI positive): m/z calcd. for C22H16Cl4N5 [M+H]+: 490.01543; Found:
490.01549.
1-Methyl-1H-benzo[d]imidazole (5a). A mixture of 1a (0.2 mmol, 33.3 mg), 2a
(0.2 mmol, 18 μL), Pd(OAc)2 (0.005 mmol, 1.1 mg), BINAP (0.005 mmol, 3.1 mg),
NaH (60% dispersed in mineral oil, 0.2 mmol, 8.0 mg) and toluene (0.5 mL) provided
5a (0.082 mmol, 10.8 mg) in 41% yield. White solid: m.p. 60.5-61.8℃. 1H NMR (500
MHz, CDCl3) δ 7.88 (s, 1H), 7.83 (d, J = 7.9 Hz, 1H), 7.42 (d, J = 7.5 Hz, 1H), 7.38 –
7.28 (m, 2H), 3.86 (s, 3H). 13C NMR (126 MHz, DMSO-d6) δ 139.0, 138.8, 129.8,
118.2, 117.3, 115.5, 104.6, 26.2. HR-MS (ESI positive): m/z calcd. for C8H9N2
[M+H]+: 133.07602; Found: 133.07605.
1-Methyl-N-(1-methyl-1H-benzo[d]imidazol-2-yl)-N-(4-phenoxyphenyl)-1H-benzo[
d]imidazol-2-amine (7a). A mixture of 1a (0.2 mmol, 33.3 mg), 6a (0.1 mmol, 18.5
mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and toluene (0.5 mL)
provided 7a (0.072 mmol, 32.1 mg) in 72% yield. White powder: m.p. 211.5-212.3℃.
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1H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 8.6 Hz, 2H), 7.41 – 7.34 (m, 2H), 7.34 –
7.25 (m, 6H), 7.14 (ddd, J = 7.4, 7.2, 1.1 Hz, 1H), 7.09 – 7.05 (m, 2H), 7.04 (d, J =
13
2.4 Hz, 4H), 3.53 (s, 6H). C NMR (126 MHz, CDCl3) δ 156.8, 154.5, 149.7, 141.1,
138.5, 135.0, 129.8, 123.5, 123.2, 122.5, 122.3, 119.9, 119.5, 119.0, 109.1, 30.2.
HR-MS (ESI): m/z calcd. for C28H24N5O [M+H]+: 446.19754; Found: 446.19727.
N-(4-(2,4-Dichlorophenoxy)phenyl)-1-methyl-N-(1-methyl-1H-benzo[d]imidazol-2-
yl)-1H-benzo[d]imidazol-2-amine (7b). A mixture of 1a (0.2 mmol, 33.3 mg), 6b (0.1
mmol, 25.4 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4 mg) and
toluene (0.5 mL) provided 7b (0.083 mmol, 42.7 mg) in 83% yield. White powder:
m.p. 217.5-218.9 ℃. 1H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 7.1 Hz, 2H), 7.49 (d,
J = 2.5 Hz, 1H), 7.35 – 7.29 (m, 5H), 7.28 – 7.26 (m, 1H), 7.23 (dd, J = 8.8, 2.5 Hz,
1H), 7.08 – 6.91 (m, 5H), 3.52 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 153.7, 151.2,
149.6, 141.2, 139.2, 135.1, 130.6, 129.4, 128.1, 126.6, 123.2, 122.7, 122.4, 121.4,
119.6, 119.3, 109.1, 30.2. HR-MS (ESI positive): m/z calcd. for C28H22Cl2N5O
[M+H]+: 514.11959; Found: 514.11934.
N-(3-Chloro-4-(2,4-dichlorophenoxy)phenyl)-1-methyl-N-(1-methyl-1H-benzo[d]i
midazol-2-yl)-1H-benzo[d]imidazol-2-amine (7c). A mixture of 1a (0.2 mmol, 33.3
mg), 6c (0.1 mmol, 28.9 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4
mg) and toluene (0.5 mL) provided 7c (0.065 mmol, 35.6 mg) in 65% yield. White
1
powder: m.p. 177.5-178.2℃. H NMR (500 MHz, CDCl3) δ 7.73 (d, J = 7.6 Hz, 2H),
7.49 (d, J = 2.6 Hz, 1H), 7.38 – 7.29 (m, 6H), 7.22 (dd, J = 8.8, 2.4 Hz, 1H), 7.17 (s,
1H), 6.90 (s, 2H), 6.87 (d, J = 8.9 Hz, 1H), 3.57 (s, 6H). 13C NMR (126 MHz, CDCl3)
δ 151.1, 148.7, 148.6, 141.1, 140.5, 135.0, 130.6, 129.3, 128.0, 126.7, 125.7, 123.2,
123.0, 122.7, 120.8, 120.4, 119.9, 119.8, 109.4, 30.2. HR-MS (ESI positive): m/z
calcd. for C28H21Cl3N5O [M+H]+: 548.08062; Found: 548.07989.
N-(3,5-dichloro-4-(2,4-dichlorophenoxy)phenyl)-1-methyl-N-(1-methyl-1H-benzo[d
]imidazol-2-yl)-1H-benzo[d]imidazol-2-amine (7d). A mixture of 1a (0.2 mmol, 33.3
mg), 6d (0.1 mmol, 32.3 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4
mg) and toluene (0.5 mL) provided 7d (0.075 mmol, 43.7 mg) in 75% yield. White
powder: m.p. 205.1-206.4℃. 1H NMR (500 MHz, CDCl3) δ 7.81 – 7.73 (m, 2H), 7.48
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(d, J = 2.5 Hz, 1H), 7.41 – 7.30 (m, 6H), 7.15 (dd, J = 8.8, 2.5 Hz, 1H), 7.02 (s, 2H),
13
6.55 (d, J = 8.8 Hz, 1H), 3.66 (s, 6H). C NMR (126 MHz, CDCl3) δ 151.0, 147.4,
143.0, 142.1, 140.9, 134.9, 130.6, 130.5, 128.0, 127.5, 123.4, 123.4, 122.9, 120.0,
119.9, 115.3, 109.6, 30.3. HR-MS (ESI): m/z calcd. for C28H20Cl4N5O [M+H]+:
582.04165; Found: 582.04100.
N-(3,5-Dichloro-4-(2-chloro-4-(trifluoromethyl)phenoxy)phenyl)-1-methyl-N-(1-me
thyl-1H-benzo[d]imidazol-2-yl)-1H-benzo[d]imidazol-2-amine (7e). A mixture of 1a
(0.2 mmol, 33.3 mg), 6e (0.1 mmol, 35.7 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3
(0.4 mmol, 130.4 mg) and toluene (0.5 mL) provided 7e (0.032 mmol, 19.7 mg) in
32% yield. White powder: m.p. 197.2-198.7 ℃. 1H NMR (500 MHz, CDCl3) δ 7.77 (d,
J = 7.6 Hz, 3H), 7.45 (dd, J = 8.7, 2.1 Hz, 1H), 7.42 – 7.30 (m, 6H), 7.04 (s, 2H), 6.70
(d, J = 8.7 Hz, 1H), 3.67 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 154.6, 147.3, 142.6,
142.5, 140.9, 134.9, 130.6, 128.2 (q, J = 3.6 Hz), 125.9 (q, J = 33.6 Hz), 125.0 (q, J =
3.5 Hz), 123.5, 123.3 (q, J = 272.0 Hz), 123.2, 123.0, 120.0, 120.0, 114.5, 109.7, 30.3.
HR-MS (ESI positive): m/z calcd. for C29H20Cl3F3N5O [M+H]+: 616.06800; Found:
616.06749.
N-(4-(2,4-Dichlorophenoxy)-3,5-difluorophenyl)-1-methyl-N-(1-methyl-1H-benzo[d
]imidazol-2-yl)-1H-benzo[d]imidazol-2-amine (7f). A mixture of 1a (0.2 mmol, 33.3
mg), 6f (0.1 mmol, 29.0 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4
mg) and toluene (0.5 mL) provided 7f (0.058 mmol, 31.9 mg) in 58% yield. White
powder: m.p. 193.3-194.4 ℃. 1H NMR (500 MHz, CDCl3) δ 7.76 (d, J = 7.7 Hz, 2H),
7.46 (d, J = 2.5 Hz, 1H), 7.41 – 7.31 (m, 6H), 7.16 (dd, J = 8.9, 2.5 Hz, 1H), 6.77 (d, J
= 8.8 Hz, 1H), 6.63 (d, J = 8.9 Hz, 2H), 3.69 (s, 6H). 13C NMR (126 MHz, CDCl3) δ
156.3 (dd, J = 252.3, 6.1 Hz), 152.1, 147.2, 141.9 (t, J = 10.9 Hz), 140.9, 134.9, 130.4,
128.4, 127.6, 127.0 (t, J = 15.3 Hz), 123.7, 123.5, 122.9, 120.0, 116.1, 109.6, 103.6
(dd, J = 21.3, 6.3 Hz), 30.3. HR-MS (ESI positive): m/z calcd. for C28H20Cl2F2N5O
[M+H]+: 550.10075; Found: 550.10102.
N-(3-Chloro-4-(2,4,6-trichlorophenoxy)phenyl)-1-methyl-N-(1-methyl-1H-benzo[d]
imidazol-2-yl)-1H-benzo[d]imidazol-2-amine (7g). A mixture of 1a (0.2 mmol, 33.3
mg), 6g (0.1 mmol, 32.3 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4
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mg) and toluene (0.5 mL) provided 7g (0.084 mmol, 49.0 mg) in 84% yield. White
powder: m.p. 212.5-213.8 ℃. 1H NMR (500 MHz, CDCl3) δ 7.69 (d, J = 7.4 Hz, 2H),
7.41 (s, 2H), 7.32 – 7.26 (m, 6H), 7.18 (d, J = 2.7 Hz, 1H), 6.77 (dd, J = 8.9, 2.8 Hz,
13
1H), 6.43 (d, J = 8.9 Hz, 1H), 3.50 (s, 6H). C NMR (126 MHz, CDCl3) δ 148.2,
147.9, 145.1, 140.1, 138.1, 134.0, 130.6, 129.2, 128.2, 123.2, 122.7, 121.9, 121.6,
119.3, 118.7, 114.3, 108.3, 29.2. HR-MS (ESI positive): m/z calcd. for C28H20Cl4N5O
[M+H]+: 582.04165; Found: 582.04178.
N-(3,5-dichloro-4-(2,4,6-trichlorophenoxy)phenyl)-1-methyl-N-(1-methyl-1H-benzo
[d]imidazol-2-yl)-1H-benzo[d]imidazol-2-amine (7h). A mixture of 1a (0.2 mmol,
33.3 mg), 6h (0.1 mmol, 35.7 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol,
130.4 mg) and toluene (0.5 mL) provided 7h (0.08 mmol, 49.4 mg) in 80% yield.
White powder: m.p. 216.0-217.5℃. 1H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 7.6 Hz,
2H), 7.34 (d, J = 4.1 Hz, 4H), 7.32 – 7.27 (m, 4H), 6.90 (s, 2H), 3.62 (s, 6H). 13C
NMR (126 MHz, CDCl3) δ 147.7, 147.4, 144.9, 141.0, 140.3, 135.0, 129.4, 129.1,
127.9, 127.1, 123.3, 122.8, 120.3, 119.9, 109.6, 30.3. HR-MS (ESI): m/z calcd. for
C28H19Cl5N5O [M+H]+: 616.00268; Found: 616.00209.
N-(3,5-Difluoro-4-(2,4,6-trichlorophenoxy)phenyl)-1-methyl-N-(1-methyl-1H-benzo
[d]imidazol-2-yl)-1H-benzo[d]imidazol-2-amine (7i). A mixture of 1a (0.2 mmol,
33.3 mg), 6i (0.1 mmol, 32.5 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol,
130.4 mg) and toluene (0.5 mL) provided 7i (0.052 mmol, 30.4 mg) in 52% yield.
White powder: m.p. 234.5-235.9 ℃. 1H NMR (500 MHz, CDCl3) δ 7.71 (d, J = 7.6 Hz,
2H), 7.38 – 7.27 (m, 8H), 6.52 (d, J = 9.3 Hz, 2H), 3.63 (s, 6H). 13C NMR (126 MHz,
CDCl3) δ 154.5 (dd, J = 250.7, 6.1 Hz), 148.0, 147.6, 141.0, 139.7 (t, J = 10.9 Hz),
135.0, 130.5, 129.7 (t, J = 10.6 Hz), 128.9, 128.4, 123.3, 122.8, 120.0, 109.6, 103.9 (d,
J = 26.6 Hz), 30.3. HR-MS (ESI positive): m/z calcd. for C28H19Cl3F2N5O [M+H]+:
584.06178; Found: 584.06130.
N-(3,5-Difluoro-4-(naphthalen-2-yloxy)phenyl)-1-methyl-N-(1-methyl-1H-benzo[d]
imidazol-2-yl)-1H-benzo[d]imidazol-2-amine (7j). A mixture of 1a (0.2 mmol, 33.3
mg), 6j (0.1 mmol, 27.1 mg), PdCl2 (0.005 mmol, 0.9 mg), Cs2CO3 (0.4 mmol, 130.4
mg) and toluene (0.5 mL) provided 7j (0.038 mmol, 20.2 mg) in 38% yield. White
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powder: m.p. 257.0-257.6℃. Isolated yield: 38%. 1H NMR (500 MHz, CDCl3) δ 7.81
(t, J = 8.1 Hz, 2H), 7.78 – 7.68 (m, 3H), 7.46 (ddd, J = 8.2, 6.9, 1.3 Hz, 1H), 7.42 –
13
7.26 (m, 8H), 7.18 (d, J = 2.5 Hz, 1H), 6.64 (d, J = 8.8 Hz, 2H), 3.69 (s, 6H). C
NMR (126 MHz, CDCl3) δ 156.9 (dd, J = 251.7, 6.4 Hz), 155.6, 147.4, 141.4 (t, J =
11.2 Hz), 141.0, 135.0, 134.1, 130.1, 129.9, 127.7, 127.5 (t, J = 15.4 Hz), 127.1, 126.7,
124.6, 123.5, 122.9, 120.0, 117.4, 109.7, 109.7, 103.7 (dd, J = 20.1, 6.3 Hz), 30.3.
HR-MS (ESI positive): m/z calcd. for C32H24F2N5O [M+H]+: 532.19434; Found:
532.19370.
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2. Original 1H and 13C NMR spectra for 1t, 3a, 4a-4t, 5a and 7a-7j
1H NMR spectrum for 1t
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13C NMR spectrum for 1t
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
1H NMR spectrum for 3a
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13C NMR spectrum for 3a
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1H NMR spectrum for 4a
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13C NMR spectrum for 4a
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1H NMR spectrum for 4b
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13C NMR spectrum for 4b
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1H NMR spectrum for 4c
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13C NMR spectrum for 4c
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1H NMR spectrum for 4d
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13C NMR spectrum for 4d
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1H NMR spectrum for 4e
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13C NMR spectrum for 4e
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1H NMR spectrum for 4f
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13C NMR spectrum for 4f
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1H NMR spectrum for 4g
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13C NMR spectrum for 4g
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1H NMR spectrum for 4h
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13C NMR spectrum for 4h
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1H NMR spectrum for 4i
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13C NMR spectrum for 4i
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1H NMR spectrum for 4j
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13C NMR spectrum for 4j
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1H NMR spectrum for 4k
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13C NMR spectrum for 4k
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
1H NMR spectrum for 4l
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13C NMR spectrum for 4l
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10.1002/asia.201901465
Chemistry - An Asian Journal
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1H NMR spectrum for 4m
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13C NMR spectrum for 4m
S29
This article is protected by copyright. All rights reserved.