Synthesis of Five-Membered Iodine-Nitrogen Heterocycles from Benzimidazole-Based Iodonium Salts

Article abstract of DOI:10.1021/acs.joc.8b01995

Pseudocyclic 2-benzimidazolyl-substituted diaryliodonium salts were obtained by the reaction of the corresponding [hydroxy(tosyloxy)iodo]arenes with arenes in the presence of trifluoromethanesulfonic acid. X-ray structural analysis of these iodonium salts confirmed their pseudocyclic structure with a short (2.57-2.58 ?) noncovalent I···N interaction. Treatment of 2-benzimidazolyl-substituted diaryliodonium triflates with a base afforded novel five-membered iodine-nitrogen heterocycles.

Full text of DOI:10.1021/acs.joc.8b01995

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Article
Synthesis of five-membered iodine-nitrogen
heterocycles from benzimidazole-based iodonium salts
Yulia A. Vlasenko, Pavel S. Postnikov, Marina E. Trusova, Alexandr
Shafir, Viktor V Zhdankin, Akira Yoshimura, and Mekhman S. Yusubov
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01995 • Publication Date (Web): 11 Sep 2018
Downloaded from http://pubs.acs.org on September 11, 2018
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Synthesis of five-membered iodine-nitrogen heterocycles from
benzimidazole-based iodonium salts
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Yulia A. Vlasenko,† Pavel S. Postnikov,#,† Marina E. Trusova,† Alexandr Shafir,‡,$ Viktor V.
Zhdankin,*,§ Akira Yoshimura,†,§ and Mekhman S. Yusubov*,†
† The Tomsk Polytechnic University, 634050 Tomsk, Russia; e-mail: yusubov@mail.ru
# University of Chemistry and Technology, 16628 Prague, Czech Republic
‡ Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology,
Tarragona, Spain
$
Institute of Advanced Chemistry of Catalonia (IQAC-CSIC), Jordi Girona 18-26, 08034 Barcelona,
Spain
§ Department of Chemistry and Biochemistry, University of Minnesota Duluth, Duluth, Minnesota,
55812; e-mail: vzhdanki@d.umn.edu
Table of Graphic Contents
TsO–
N
+
I
OH
TfO–
N
+
I
Ar
Ar
I
R2
R1
R2
R1
KOH, MeOH
81-96%
R2
R1
ArH, TfOH
81-98%
N
N
N
H
N
H
R1 and R2 = H, Me, Cl, F, NO2
18 examples
ABSTRACT: Pseudocyclic 2-benzimidazolyl-substituted diaryliodonium salts were obtained by the
reaction of the corresponding [hydroxy(tosyloxy)iodo]arenes with arenes in the presence of
trifluoromethanesulfonic acid. X-ray structural analysis of these iodonium salts confirmed their
pseudocyclic structure with a short (2.57-2.58 Å) non-covalent I•••N interaction. Treatment of 2-
benzimidazolyl-substituted diaryliodonium triflates with a base afforded novel five-membered iodine-
nitrogen heterocycles.
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1. Introduction
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Since the beginning of the 21st century, the interest in hypervalent iodine heterocycles has
experienced an unprecedented growth.1 The five-membered iodine-oxygen heterocycles
(benziodoxoles) represent one of the most important classes of hypervalent iodine(III) reagents.1-6
Substituted benziodoxolones 1 (Scheme 1) are widely used as electrophilic or radical atom-transfer
reagents for azidation,2 amination,3 cyanation,4 alkynylation,5 or chlorination.6 Other important classes
of five-membered hypervalent iodine(III) heterocycles include dibenziodolium derivatives 2 and 3, and
benziodazolones 4. Five-membered cyclic iodonium salts 2, derivatives of the iodolium heterocyclic
system, are particularly interesting because of the high thermal stability and applications in biological
studies.7-9 For example, dibenziodolium chloride (also known as diphenyleneiodonium chloride or
DPI) has found numerous applications in biological studies.8,9 In biochemical and pharmacological
research DPI is commonly used as a NADPH oxidase inhibitor.9 The neutral dibenziodolium
derivatives, 5-aryl-5H-5λ3-dibenzo[b,d]iodoles 3, have also been prepared as thermally unstable and
air sensitive compounds.10
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The preparation of several five-membered iodine-nitrogen heterocycles, benziodazolones 4, has been
reported by Wolf and Steinberg,11 Gougoutas,12 Balthazor,13 and our group.14 Benziodazolone
derivatives can be used as reagents for oxidative functionalization of organic substrates.14a,15,16 For
example, azidobenziodazolone was used as an azidation reagent with a similar to azidobenziodoxoles
reactivity.14a Very recently, we reported the preparation of a novel bicyclic benziodazolone, which is
an efficient reagent for oxidatively assisted coupling of carboxylic acids with alcohols or amines.16 To
the best of our knowledge, all known five-membered iodine-nitrogen heterocycles have the
benziodazolone structure 4, which is characterized by the presence of the amido nitrogen in the ring. In
this paper, we report the first synthesis of a stable polycyclic benziodazole system 5, which represents
a nitrogen analog of the neutral diphenyleneiodonium system 4 (Scheme 1).
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Scheme 1. Hypervalent Iodine Heterocycles: Benziodoxoles, Dibenziodolium Derivatives, and
9
Benziodazoles.
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Previously known iodine heterocycles:
X–
X
I
O
I
+
O
1
2
benziodoxolones
X = N3, NHR, CN, alkynyl, Cl, etc.
dibenziodolium salts
X = Cl, OTf, N3, SCN, CN, Br, etc.
R
X
I
N
Ar
I
O
3
4
5-aryl-5H-5λ3-dibenzo[b,d]iodoles
benziodazolones
X = AcO, N3; R = H, alkyl, etc.
This work:
Ar
I
N
N
5
5-aryl-5H-5λ3-benzo[d]benzo[4,5]imidazo[1,2-b][1,2]iodazoles
2. Results and Discussion
We have developed an efficient three-step approach to the synthesis of benziodazole system 5
starting from readily available 2-(2-iodophenyl)-1H-benzo[d]imidazoles 6. Iodides 6 were initially
oxidized to [hydroxy(tosyloxy)iodo]arenes 7 by treatment with m-chloroperoxybenzoic acid in the
presence of p-toluenesulfonic acid (Scheme 2) according to the modified procedure of Yamamoto and
Togo.17 Products with the general structure type 7 were isolated in high yields in the form of stable
microcrystalline solids and were characterized by NMR and mass-spectrometry. According to NMR,
the non-symmetrically substituted derivatives of 7 (R1 ≠ R2) in solution exist in the form of two
tautomers differing in the position of the protonated N-site in the benziodazole fragment.
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Scheme 2. Oxidation of 2-(2-iodophenyl)-1H-benzo[d]imidazoles 6 to [hydroxy(tosyloxy)iodo]arenes
7. Bottom: X-ray structure diagram of 7a.
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TsO–
OH
m-CPBA (2.0 equiv)
TsOH·H2O (1.4 equiv)
CH2Cl2-TFE (1:1), rt
+
I
I
R2
R1
R2
R1
N
N
84-98%
N
H
N
H
6a: R1 = H, R2 = H
6b: R1 = H, R2 = NO2
6c: R1 = H, R2 = Me
6d: R1 = H, R2 = Cl
6e: R1 = Me, R2 = Me
6f: R1 = F, R2 = F
7a: R1 = H, R2 = H
7b: R1 = H, R2 = NO2
7c: R1 = H, R2 = Me
7d: R1 = H, R2 = Cl
7e: R1 = Me, R2 = Me
7f: R1 = F, R2 = F
Next, we sought to convert the newly prepared [hydroxy(tosyloxy)iodo]arenes 7 into diaryliodonium
species by a direct reaction with arenes. Initially, the model tosylate 7a demonstrated extremely low
reactivity towards arenes, and even the treatment with the electron-rich mesitylene did not lead to the
formation of desired iodonium salt 8a after 32 hours of stirring in trifluoroethanol according to Kita's
procedure.18 Nevertheless, the addition of 1.5 equivalent of TfOH led to a dramatic change in reactivity
and allowed for the isolation of the iodonium salt 8a in quantitative yield. Using this protocol, a series
of N-coordinated diaryliodonium salts 8a-r could be prepared in the presence of triflic acid, as shown
in Scheme 3. These salts were isolated in excellent yields in their N-H triflate forms and were
characterized by NMR and mass-spectrometry. The presence of a proton on one of the benzimidazole
nitrogen should in principle lead to all four benzimidazole C-H sites in 8a to be chemically distinct.
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Experimentally, the H NMR of 8a showed a fluxional behavior for the benzimidazole moiety,
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evidenced by two broad resonances each integrating for 2H, suggesting a rather rapid equilibration of
the two sides of the molecule. Similar behavior was observed for the rest for the derivatives within this
family. The solid state structures of two such salts, the nitro-derivative 8e and the chloro-derivative
8m, were subsequently determined to be borderline pseudocyclic thanks to the presence of a long
nitrogen-to-iodine donor bond (Figure 1). It should be noted that the presence of a substituent on the
benzimidazole fragment leads to the possibility of two tautomeric structures, both of which were found
to co-exist in the solid state (via disorder) and in solution.
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Scheme 3. Formation and examples of the pseudocyclic diaryliodonium species 8.
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TsO–
N
OH
+
I
TfO–
+
I
Ar
R2
R1
1. TfOH (1.5 equiv), TFE, rt, 10 min
R2
R1
N
2. ArH (2-3 equiv), 0-50 oC, 2-9 h
N
H
N
H
81-98%
7
8a-r
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Me
Me
OMe
OMe
OMe
OMe
S
TfO–
TfO–
N
TfO–
Me
TfO–
N
+
+
+
+
Me
I
I
I
I
N
N
N
H
N
H
N
H
N
H
8d, 92% (0-5 oC, 3 h)
8a, 98% (rt, 8 h)
8b, 90% (50 oC, 9 h)a
8c, 96% (0-5 oC, 2 h)
Me
Me
S
TfO–
Me
TfO–
TfO–
TfO–
+
+
+
+
Me
I
I
I
I
N
N
N
N
N
N
H
N
H
N
H
O2N
O2N
Me
O2N
Me
Cl
O2N
Me
H
8g, 86% (0-5 oC, 3 h)
8f, 88% (50 oC, 9 h)a
8e, 92% (rt, 9 h)
8h, 82% (0-5 oC, 3 h)
S
TfO–
Me
TfO–
TfO–
TfO–
+
+
+
+
Me
I
I
I
I
N
N
N
N
N
N
H
N
H
N
H
Me
Me
Me
Me
Me
H
8l, 89% (0-5 oC, 3 h)
8i, 94% (rt, 8 h)
8j, 91% (50 oC, 9 h)a
8k, 91% (0-5 oC, 2 h)
S
TfO–
Me
TfO–
TfO–
TfO–
+
+
+
+
Me
I
I
I
I
N
N
N
N
N
H
N
H
N
H
N
H
Cl
Cl
Cl
8n, 93% (50 oC, 9 h)a
8o, 89% (0-5 oC, 2 h)
8p, 81% (0-5 oC, 3 h)
8m, 84% (rt, 8 h)
OMe
Me
MeO
Me
TfO–
+
TfO–
+
OMe
Me
I
I
F
N
N
N
H
N
H
Cl
F
8q, 96% (0-5 oC, 2 h)
8r, 82% (rt, 8 h)
a Hexafluoroisopropanol (HFIP) was used as a solvent instead of trifluoroethanol (TFE).
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Figure 1. X-Ray crystal structure diagrams for 8e (left) and 8m (right). All except N-bound protons
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have been omitted for clarity.
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At this point, we wondered whether the pseudocyclic species 8 could readily form the corresponding
1
cyclic derivative upon deprotonation. This possibility was tested by examining the H NMR spectrum
of the thienyl pseudocycle 8c in DMSO-d6 before and after the addition of 1.0 equiv of KOH (Figure 2,
a and b). Consistent with our hypothesis, the addition of the base led to a significant change in the
spectrum, with benzimidazole resonances shifted upfield by up to 0.2 ppm (Figure 2, a and b). The
original chemical shifts of 8c could be largely restored by treating the resulting solution of 9c with 1.0
equivalent of TfOH (Figure 2, c), attesting to the reversibility of the cyclic-pseudocyclic
interconversion. As a synthetic procedure, treating the methanolic solution of 8c with potassium
hydroxide led to the precipitation of the cyclic 9c in nearly quantitative yield. Similarly, a series of
cyclic hypervalent iodine heterocycles 9 (Scheme 4) were isolated as thermally stable solids in
excellent yields, and were characterized by NMR and mass-spectrometry. Unfortunately, we were not
able to grow single crystals of 9 suitable for X-ray analysis.
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Scheme 4. Formation and examples of the cyclic diaryliodonium species 9.
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7
8
9
TfO–
+
Ar
Ar
I
I
R2
R1
KOH (2 equiv), MeOH, H2O, rt, 1 h
81-96%
R2
R1
N
N
N
N
H
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8
9
Me
Me
OMe
OMe
OMe
S
Me
Me
I
I
I
I
N
N
N
N
N
N
N
N
9c, 95%
9d, 94%
9a, 96%
9b, 91%
Me
Me
S
Me
Me
I
I
I
I
N
N
N
N
N
N
N
N
O2N
O2N
Me
O2N
O2N
Me
9g, 92%
9h, 86%
9e, 96%
9f, 83%
S
Me
Me
I
I
I
I
N
N
N
N
N
N
N
N
Me
Me
Me
Me
Me
Me
9i, 93%
9j, 84%
9k, 93%
9l, 83%
OMe
S
Me
Me
I
I
I
I
N
N
N
N
N
N
N
N
Cl
Cl
Cl
Cl
9m, 92%
9n, 89%
9o, 95%
9p, 91%
OMe
Me
MeO
Me
OMe
Me
I
I
F
F
N
N
N
N
Cl
9q, 85%
9r, 81%
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Figure 2. Changes observed in the 1H NMR spectrum of 8c upon addition of KOH (a and b). Bottom
spectrum (c) was recorded upon addition of TfOH (1.0 equiv) to the sample b.
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Interestingly, unlike the pseudocyclic triflates, the NMR spectra of 9 were at odds with what was
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expected for a stronger N-I bond. Hence, while the F NMR spectrum of the pseudocyclic difluoro
derivative 8r showed two aromatic fluorine resonances (doublets in the proton-decoupled mode), the
19
corresponding cyclic derivative 9r showed a unique well-defined F singlet, indicating either a low
rotation barrier around the C-C bond (Figure 3), or a preference for a Cs-symmetric non-cyclic
conformation with the ArI ring perpendicular to the benzimidazole plane.
Figure 3. The aromatic region of the 19F {1H} NMR spectra of the difluoro derivatives 8r (top) and 9r
(bottom).
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Due to the same phenomenon, the asymmetrically substituted derivatives, such as 9o, displayed an
NMR spectrum consistent with a relatively facile rotamer interconversion. In order to shed light on this
phenomenon, the conformational analysis of the chloro-substituted 9o was carried out using DFT
calculations. It was found that the two cyclic forms do indeed represent the energetic minima, and the
non-cyclic perpendicular form a transition state in rotamer interconversion (Figure 4). The “proximal”
isomer proved to be somewhat more stable (about ~2 kcal/mol) than the “remote” one, with an
interconversion barrier of ~16 kcal/mol consistent with a medium velocity rotamer interconversion on
the NMR timescale. For comparison, the barrier for a degenerate exchange (via C-N) bond rotation in
N,N-dimethylformamide is close to ΔG‡ ~19 kcal/mol.19 Interestingly, in the case of the pseudo cyclic
derivatives such as 8o, the apparently higher barrier for tautomerization may seem contrary to what
would be expected for a weaker I-N bond. It should be noted, however, that while the tautomerization
in 9o may be achieved by a simple rotation (as shown in Figure 4), such process in 8o is precluded due
to the protonation at the “remote” nitrogen atom. Hence, tautomerization in this case likely proceeds in
a multistep sequence involving both a proton transfer and a rotation. In consequence, such process
would be more difficult to model, and may show a strong medium dependence.
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Figure 4. Energy profile for the rotamer interconversion of a cyclic benzimidazole-containing system.
Values are given in kcal/mol: DFT: B3LYP, 6-31+G(d,p)/ LANL2DZ(d,p) for I.
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3. Conclusions
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In summary, we have reported the synthesis of a novel, stable hypervalent iodine polyheterocyclic
system derived from benziodazole. The hypervalent iodine heterocycles 9 were prepared starting from
readily available 2-(2-iodophenyl)-1H-benzo[d]imidazoles 6 via benzimidazole-based diaryliodonium
salts 8. The prepared iodazoles exhibit a fast interconversion between tautomers according to NMR
experiment and theoretical calculations.
EXPERIMENTAL SECTION
General Comments.
All reagents and solvents were from commercial sources and used without further purification from
1
freshly opened containers. H NMR spectra were recorded at 400 MHz and 500 MHz; 13C NMR
spectra were recorded at 100 MHz and 125 MHz; 19F NMR spectra were recorded at 376 MHz.
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Chemical shifts are reported in parts per million (ppm). H and 13C chemical shifts are referenced
relative to tetramethylsilane. High resolution mass-spectra were recorded on Thermo Fisher Scientific
LC-MS LTQ-Orbitrap Velos and MicroTof-Q from Bruker daltronics instruments with electrospray
ionization (EI) in positive ionization mode.
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Synthesis of Benzimidazoles 6: General Procedure. Benzimidazoles 6a-6f were prepared according to
a slightly modified published procedure.20
The mixture of appropriate o-phenylenediamine (20 mmol) and 2-iodobenzoic acids (20 mmol, 5.6 g)
in polyphosphoric acid (200 mmol, 30.2 g) was heated to 100 °С. POCl3 (65 mmol, 9.87 g, 6 ml) was
added portionwise (1 ml every 15 minutes) to a stirred reaction mixture at 100 °С. The heating was
continued until full conversion of starting material (monitored by TLC, eluent hexane: EtOAc = 2:7).
The reaction mixture was cooled to room temperature with the formation of solid material. The solid
was suspended in water (70 mL) and was basified by the addition of solid NaHCO3 until pH = 7-8. The
precipitate was filtered-off and washed on filter with water 30 mL and recrystallized from water-
ethanol mixture. In case of 5,6-difluoro-2-(2-iodophenyl)-1H-benzimidazole, the precipitate was
filtered off, re-suspended in 600 mL of EtOAc and filtered through a short pad of celite. The solvent
was removed under reduced pressure at room temperature.
2-(2-Iodophenyl)-1H-benzo[d]imidazole (6a)
I
N
N
H
Reaction of o-phenylenediamine (2.16 g, 20 mmol) according to the general procedure afforded 5.12 g
(80%) of product 6a, isolated as a linen solid: mp 246−247 °C (lit.21, mp 230−232 °C); 1H NMR (500
MHz, DMSO-d6): δ = 12.70 (s, 1H), 8.06 (dd, J = 8.0, 1,0 Hz, 1H), 7.62 (d, J = 7.5 Hz, 1H), 7.62 (dd,
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J = 7.5, 1.5 Hz, 1H), 7.57-7.53 (m, 2H), 7.29-7.20 (m, 3H); 13C NMR (125 MHz, DMSO-d6): δ =
5
6
7
8
152.6, 143.2, 139.6, 136.6, 134.3, 131.3, 131.1, 128.1, 122.5, 121.4, 119.1, 111.5, 97.3.
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2-(2-Iodophenyl)-6-nitro-1H-benzo[d]imidazole (6b)
I
I
H
N
N
N
H
N
O2N
O2N
Reaction of 4-nitrobenzene-1,2-diamine (3.06 g, 20 mmol) according to the general procedure afforded
5.69 g (78%) of product 6b (mixture of tautomers) , isolated as a dark-orange solid: mp 207−208 °C;
1H NMR (400 MHz, DMSO-d6): δ = 10.20 (d, J = 5.6 Hz, 1H), 8.74 (s, 1H), 8.54 (s, 1H), 8.18 (d, J =
8.8 Hz, 1H), 8.09 (d, J = 7.6 Hz, 1H), 7.95 (d, J = 7.2 Hz, 1H), 7.81 (d, J = 8.8 Hz, 1H), 7.67 (d, J =
7.6 Hz, 1H), 7.60 (t, J = 7.6 Hz, 1H), 7.52 (t, J = 7.6 Hz, 1H), 7.34 (t, J = 7.6 Hz, 1H), 7.25 (t, J = 7.2
Hz, 1H); 13C NMR (100 MHz, DMSO-d6): δ = 157.1, 143.5, 142.8, 142.0, 141.9, 139.8, 139.2, 139.1,
136.1, 135.5, 131.9, 131.6, 131.4, 128.4, 128.3, 124.5, 120.7, 120.0, 118.1, 114.9, 112.7, 97.2; HRMS
(ESI-TOF-positive ionization): calcd for C13H9IN3O2 ([M+H]+): 365.9734, found: 365.9738. The
crystal suitable for X-ray was prepared by slow evaporation of MeCN/H2O solution (the structure is
provided in SI).
2-(2-Iodophenyl)-6-methyl-1H-benzo[d]imidazole (6c)
I
I
H
N
N
N
H
N
Me
Me
Reaction of 4-methylbenzene-1,2-diamine (2.44 g, 20 mmol) according to the general procedure
afforded 5.41 g (81%) of product 6c (mixture of tautomers), isolated as a beige solid: mp 85−86 °C; 1H
NMR (400 MHz, DMSO-d6): δ = 12.59 (s, 1H), 8.05 (d, J = 7.6 Hz, 1H), 7.60 (dd, J = 7.6, 1.6 Hz,
1H), 7.54 (t, J = 7.6 Hz, 1H), 7.49 (d, J = 8.4 Hz, 1H), 7.38 (s, 1H), 7.26 (td, J = 7.6, 1.6 Hz, 1H), 7.05
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(d, J = 8.0 Hz, 1H), 2.43 (s, 3H); C NMR (100 MHz, DMSO-d6): δ = 152.5, 152.1, 143.6, 141.4,
139.7, 136.7, 134.7, 132.4, 131.9, 131.3, 131.1, 130.5, 128.1, 124.0, 123.1, 118.9, 118.7, 111.2, 111.0,
97.4, 21.4, 21.3; HRMS (ESI-TOF-positive ionization): calcd for C14H12IN2 ([M+H]+): 335.0040,
found: 335.0041.
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6-Chloro-2-(2-iodophenyl)-1H-benzo[d]imidazole (6d)
I
I
H
N
N
N
H
N
Cl
Cl
Reaction of 4-chlorobenzene-1,2-diamine (2.85 g, 20 mmol) according to the general procedure
afforded 6.03 g (85%) of product 6d (mixture of tautomers), isolated as a creamy-white solid: mp
189−190 °C;1H NMR (400 MHz, DMSO-d6): δ = 12.91 (d, J = 11.6 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H),
7.76 (s, 1H), 7.71 (d, J = 8.4 Hz, 1H), 7.62 (d, J = 7.6 Hz, 1H), 7.58-7.54 (m, 2H); 7.31-7.23 (m, 2H);
13C NMR (100 MHz, DMSO-d6): δ = 154.1, 153.7, 144.0, 141.9, 139.7, 136.1, 135.0, 133.1, 131.4,
131,3, 128.1, 126.9, 126.0, 122.7, 121.9, 120.4, 118.5, 112.8, 111.2, 97.2; HRMS (ESI-TOF-positive
ionization): calcd for C13H9ClIN2 ([M+H]+): 354.9493, found: 354.9494.
2-(2-Iodophenyl)-5,6-dimethyl-1H-benzo[d]imidazole (6e)
I
Me
N
N
H
Me
Reaction of 4,5-dimethylbenzene-1,2-diamine (2.72 g, 20 mmol) according to the general procedure
afforded 5.50 g (79%) of product 6e, isolated as a beige solid: mp 203−204 °C;1H NMR (400 MHz,
DMSO-d6): δ = 12.41 (s, 1H), 8.04 (d, J = 8.0 Hz, 1H), 7.59 (dd, J = 7.6, 1.6 Hz, 1H), 7.53 (td, J = 7.6,
0.8 Hz, 1H), 7.44 (s, 1H), 7.28-7.23 (m, 2H), 2.33 (s, 6H); 13C NMR (100 MHz, DMSO-d6): δ = 152.1,
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142.4, 140.1, 137.2, 133.4, 131.7, 131.6, 131.4, 130.2, 128.5, 119.6, 111.9, 97.8, 20.5; HRMS (ESI-
TOF-positive ionization): calcd for C15H14IN2 ([M+H]+): 349.0196, found: 349.0198.
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5,6-Difluoro-2-(2-iodophenyl)-1H-benzo[d]imidazole (6f)
I
F
N
N
H
F
Reaction of 4,5-difluorobenzene-1,2-diamine (2.88 g, 20 mmol) according to the general procedure
1
afforded 4.98 g (70%) of product 6f, isolated as a deep violet solid: mp 186−187 °C; H NMR (400
MHz, DMSO-d6): δ = 8.06 (d, J = 7.6 Hz, 1H), 7.70 (t, J = 9.2 Hz, 2H), 7.62 (dd, J = 7.6, 1.6 Hz, 1H),
13
7.56 (t, J = 7.2 Hz, 2H), 7.30 (td, J = 7.6, 1.6 Hz, 1H); C NMR (100 MHz, DMSO-d6): δ = 154.49,
154.48, 154.46, 148.2 (d, JC-F = 16.4 Hz), 145.8 (d, JC-F = 16.4 Hz), 139.7, 135.7, 131.6, 131.4, 128.2,
103.1 (br. s), 97.4; 19F NMR (376 MHz, DMSO-d6): δ = -143.7; HRMS (ESI-TOF-positive
ionization): calcd for C13H8F2IN2 ([M+H]+): 356.9695, found: 356.9700.
Synthesis of [Hydroxy(tosyloxy)iodo]arenes 7: General Procedure.
To a stirred solution of 2-(2-iodophenyl)-1H-benzo[d]imidazoles 6a-6f (1.0 equiv) in a mixture of
DCM-TFE (1:1) was added mCPBA (77%, 2.0 equiv) and p-TsOH•H2O (1.4 equiv). The stirring was
continued at room temperature until full conversion of starting material (monitored by TLC, eluent
hexane: EtOAc = 2:7), and solvents was evaporated at reduced pressure. The products were
precipitated by the addition of Et2O. The solids were filtered off, washed with Et2O three times and
dried in a vacuum.
(2-(1H-Benzo[d]imidazol-2-yl)phenyl)(hydroxy)iodonium tosylate (7a)
TsO–
OH
+
I
N
N
H
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Reaction of 2-(2-iodophenyl)-1H-benzo[d]imidazole 6a (1.60 g, 5 mmol) with mCPBA (77%, 3.46 g,
10 mmol) and p-TsOH•H2O (1.33 g, 7 mmol) in 25 mL of DCM-TFE mixture (1:1) according to the
general procedure afforded 2.49 g (98%) of product 7a, isolated as a beige solid: mp 190−192 °C; 1H
NMR (300 MHz, DMSO-d6): δ = 8.44 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 8.1 Hz, 1H), 7.99-7.87 (m, 3H),
7.78-7.75 (m, 1H), 7.51-7.46 (m, 4H), 7.11 (d, J = 8.1 Hz, 2H), 2.26 (s, 3H); 13C NMR (75 MHz,
DMSO-d6): δ = 151.3, 145.2, 138.4, 136.7, 134.2, 131.5, 128.5, 128.2, 128.0, 125.8, 125.7, 125.3,
124.8, 121.1, 117.1, 113.7, 21.0; HRMS (ESI-TOF-positive ionization): calcd for C13H10IN2O ([M-
OTs]+): 336.9838, found: 336.9832. The crystal suitable for X-ray was prepared by slow cooling of
saturated MeCN/H2O solution followed by evaporation.
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Hydroxy(2-(6-nitro-1H-benzo[d]imidazol-2-yl)phenyl)iodonium tosylate (7b)
TsO–
TsO–
OH
OH
+
I
+
I
O2N
N
N
N
H
N
H
O2N
Reaction of 2-(2-iodophenyl)-1H-benzo[d]imidazole 6b (1.83 g, 5 mmol) with mCPBA (77%, 3.46 g,
10 mmol) and p-TsOH•H2O (1.33 g, 7 mmol) in 25 mL of DCM-TFE mixture (1:1) according to the
general procedure afforded 2.49 g (90%) of product 7b (mixture of tautomers), isolated as a yellow
solid: mp 220−221 °C; 1H NMR (400 MHz, DMSO-d6): δ = 9.00 (d, J = 1.6 Hz, 1H), 8.61 (s, 1H),
8.55-8.51 (m, 2H), 8.32-8.30 (m, 2H), 8.12-8.09 (m, 2H), 8.05-7.93 (m, 4H), 7.49 (d, J = 7.6 Hz, 3H),
7.11 (d, J = 8.0 Hz, 3H), 2.28 (s, 4H); 13C NMR (100 MHz, DMSO-d6): δ = 145.4, 144.1, 143.0, 141.3,
140.0, 139.2, 138.2, 136.5, 134.9, 133.6, 132.2, 131.6, 130.9, 129.0, 128.8, 128.4, 127.9, 127.7, 125.7,
125.1, 121.4, 121.3, 120.6, 119.9, 118.4, 117.5, 114.6, 113.7, 110.6, 21.0; HRMS (ESI-TOF-positive
ionization): calcd for C13H9IN3O3 ([M-OTs]+): 381.9689, found: 381.9685.
Hydroxy(2-(6-methyl-1H-benzo[d]imidazol-2-yl)phenyl)iodonium tosylate (7c)
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TsO–
N
TsO–
OH
OH
+
I
+
I
Me
N
N
H
N
H
Me
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Reaction of 2-(2-iodophenyl)-1H-benzo[d]imidazole 6c (1.67 g, 5 mmol) with mCPBA (77%, 3.46 g,
10 mmol) and p-TsOH•H2O (1.33 g, 7 mmol) in 25 mL of DCM-TFE mixture (1:1) according to the
general procedure afforded 2.19 g (84%) of product 7c (mixture of tautomers), isolated as a creamy-
white solid: mp 175-176 °C; 1H NMR (400 MHz, DMSO-d6): δ = 14.52 (br. s, 1H), 14.46 (br. s, 1H),
8.44 – 8.41 (m, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.93 (t, J = 7.2 Hz, 1H), 7.87 (t, J = 7.6 Hz, 1H), 7.79 (d,
J = 8.4 Hz, 1H), 7.71 (s, 1H), 7.62 (d, J = 8.4 Hz, 1H), 7.53-7.48 (m, 3H), 7.24 (t, J = 8.0 Hz, 1H), 7.11
(d, J = 8.0 Hz, 2H), 2.44 (d, J = 6.4 Hz, 3H), 2.27 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ = 150.8,
150.6, 145.3, 138.0, 136.7, 135.4, 134.6, 134.2, 134.1, 133.7, 133.6, 132.0, 131.2, 128.2, 127.9, 127.7,
126.9, 126.0, 125.6, 125.2, 120.9, 120.8, 116.4, 116.3, 113.1, 112.9, 21.4, 21.3, 20.8; HRMS (ESI-
TOF-positive ionization): calcd for C14H12IN2O ([M-OTs]+): 350.9994, found: 350.9994.
(2-(6-Chloro-1H-benzo[d]imidazol-2-yl)phenyl)(hydroxy)iodonium tosylate (7d)
TsO–
TsO–
OH
OH
+
+
I
I
Cl
N
N
N
H
N
H
Cl
Reaction of 2-(2-iodophenyl)-1H-benzo[d]imidazole 6d (1.77 g, 5 mmol) with mCPBA (77%, 3.46 g,
10 mmol) and p-TsOH•H2O (1.33 g, 7 mmol) in 25 mL of DCM-TFE mixture (1:1) according to the
general procedure afforded 2.61 g (96%) of product 7d (mixture of tautomers), isolated as a beige
solid: mp 188−190 °C; 1H NMR (400 MHz, DMSO-d6): δ = 9.22 (br. s, 1H), 8.44 (t, J = 6.8 Hz, 1H),
8.05 (d, J = 8.4 Hz, 2H), 7.98-7.86 (m, 3H), 7.80 (s, 1H), 7.77 (d, J = 8.8 Hz, 1H), 7.52 (d, J = 8.0 Hz,
2H), 7.45 (d, J = 8.8 Hz, 1H), 7.12 (d, J = 7.6 Hz, 2H), 2.27 (s, 3H); 13C NMR (100 MHz, DMSO-d6):
δ = 152.3, 145.1, 138.1, 137.4, 135.6, 134.8, 134.2, 134.1, 133.0, 131.3, 129.8, 128.7, 128.3, 127.7,
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127.6, 125.6, 125.0, 124.9, 121.0, 120.9, 118.3, 116.6, 115.0, 113.3, 20.9; HRMS (ESI-TOF-positive
ionization): calcd for C13H8ClIN2 ([M-OH-OTs]+): 353.9415, found: 353.9415.
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(2-(5,6-Dimethyl-1H-benzo[d]imidazol-2-yl)phenyl)(hydroxy)iodonium tosylate (7e)
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TsO–
OH
+
I
Me
N
N
H
Me
Reaction of 2-(2-iodophenyl)-1H-benzo[d]imidazole 6e (0.70 g, 2 mmol) with mCPBA (77%, 1.38 g, 4
mmol) and p-TsOH•H2O (0.53 g, 2.8 mmol) in 10 mL of DCM-TFE mixture (1:1) according to the
general procedure afforded 0.97 g (91%) of product 7e, isolated as a beige solid: mp 185−186 °C; 1H
NMR (400 MHz, DMSO-d6): δ = 14.40 (s, 1H), 8.44 (dd, J = 7.6, 1.6 Hz, 1H), 8.08 (d, J = 7.6 Hz,
1H), 7.95 (td, J = 7.6, 1.6 Hz, 1H), 7.90 (td, J = 7.6, 1.2 Hz, 1H), 7.71 (s, 1H), 7.54 (s, 1H), 7.49 (d, J =
13
8.0 Hz, 1H), 7.11 (d, J = 7.6 Hz, 1H), 2.39 (s, 3H), 2.37 (s, 3H) 2.28 (s, 3H); C NMR (100 MHz,
DMSO-d6): δ = 150.1, 145.6, 137.7, 135.0, 134.9, 134.0, 133.5, 132.4, 131.2, 128.1, 127.7, 125.5,
125.3, 120.7, 116.5, 113.1, 20.8, 20.1, 20.0; HRMS (ESI-TOF-positive ionization): calcd for
C15H13IN2 ([M-OH-OTs]+): 348.0118, found: 348.0120.
(2-(5,6-Difluoro-1H-benzo[d]imidazol-2-yl)phenyl)(hydroxy)iodonium tosylate (7f)
TsO–
OH
+
I
F
N
N
H
F
Reaction of 2-(2-iodophenyl)-1H-benzo[d]imidazole 6f (0.71 g, 2 mmol) with mCPBA (77%, 1.38 g, 4
mmol) and p-TsOH•H2O (0.53 g, 2.8 mmol) in 10 mL of DCM-TFE mixture (1:1) according to the
general procedure afforded 0.95 g (87%) of product 7f, isolated as a light brown solid: mp 167−168
°C; 1H NMR (400 MHz, DMSO-d6): δ = 8.48 (dd, J = 7.6, 1.2 Hz, 1H), 8.08-8.03 (m, 2H), 8.00-7.96
(m, 2H), 7.91 (td, J = 7.5, 0.8 Hz, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.11(d, J = 7.6 Hz, 2H), 2.28 (s, 3H);
13C NMR (100 MHz, DMSO-d6): δ =153.0, 145.5, 139.7, 137.9, 134.1, 132.5 (d, JC-F = 11.7 Hz),
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5
6
7
8
9
19
102.1 (d, JC-F = 23.1 Hz), 20.8; F NMR (376 MHz, DMSO-d6): δ = -138.6 (d, J = 23.2 Hz), -139.9
(d, J = 23.2 Hz); HRMS (ESI-TOF-positive ionization): calcd for C13H7F2IN2 ([M-OH-OTs]+):
355.9616, found: 355.9621.
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Synthesis of (2-(1H-benzo[d]imidazol-2-yl)phenyl)(aryl)iodonium triflates 8: General Procedure.
To a stirred solution of [hydroxy(tosyloxy)iodo]arenes 7a-7f (0.2 mmol, 1 equiv) in 1.5 mL TFE or
HFIP were added trifluoromethanesulfonic acid (0.026 mL, 0.3 mmol, 1.5 equiv) and reaction mixture
was stirred during 10 min. Then arene was added and stirring was continued until full conversion of
starting material according to NMR (temperature and reaction times are provided in the text). The
solvent was evaporated at room temperature. The products were precipitated by the addition of Et2O.
The solids were filtered off, washed with Et2O three times and dried in a vacuum.
(2-(1H-Benzo[d]imidazol-2-yl)phenyl)(mesityl)iodonium triflate (8a)
Me
Me
TfO–
+
Me
I
N
N
H
Reaction of [hydroxy(tosyloxy)iodo]arene 7a (0.102 g, 0.2 mmol) with mesitylene (0.056 mL, 0.048 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at room temperature during 8 h afforded
0.115 g (98%) of product 8a, isolated as a beige solid: mp 195−196 °C; 1H NMR (400 MHz, DMSO-
d6) δ = 13.90 (s, 1H), 8.47 (dd, J = 7.6, 1.6 Hz, 1H), 7.86 (t, J = 7.2 Hz, 1H), 7.78 - 7.76 (m, 2H), 7.60 -
7.56 (m, 1H), 7.44-7.40 (m, 2H), 7.37 (s, 2H), 6.92 (d, J = 8.0 Hz, 1H), 2.53 (s, 6H), 2.42 (s, 3H); 13C
NMR (125 MHz, DMSO-d6): δ = 149.3, 144.0, 143.0, 133.8, 131.4, 130.0, 129.4, 128.9, 127.8, 124,2,
124.1, 121.0, 120.71 (q, JCF = 320 Hz, CF3SO3 ), 111.6, 26.0, 20.8; 19F NMR (376 MHz, DMSO-d6): δ
-
= -77.7; HRMS (ESI-TOF-positive ionization): calcd for C22H20IN2 ([M-OTf]+): 439.0671, found:
439.0666.
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(2-(1H-Benzo[d]imidazol-2-yl)phenyl)(p-tolyl)iodonium triflate (8b)
6
7
Me
8
9
TfO–
+
I
10
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N
N
H
Reaction of [hydroxy(tosyloxy)iodo]arene 7a (0.102 g, 0.2 mmol) with toluene (0.064 mL, 0.055 g, 0.6
mmol) in 1.5 mL TFE (HFIP) according to the general procedure at 50 °C during 48 h (9 h with HFIP)
afforded 0.092 g (82%) [or 0.101 g (90%) with HFIP] of product 8b (contains 20% of o-isomer),
isolated as a beige solid: mp 234−235 °C; 1H NMR (400 MHz, DMSO-d6) δ = 13.93 (s, 1H), 8.45 (dd,
J = 8.0, 1.2 Hz, 1H), 8.36 (d, J = 7.6 Hz, 1H), 8.21 (d, J = 8.0 Hz, 2H), 7.84 (t, J = 7.2 Hz, 1H), 7.80
(d, J = 7.2 Hz, 1H), 7.74 (dd, J = 7.6, 1.6 Hz, 1H), 7.63 – 7.57 (m, 1H), 7.54 (d, J = 8.0 Hz, 2H), 7.49 –
7.46 (m, 1H), 7.42 (td, J = 7.2, 1.2 Hz, 2H), 7.11 (d, , J = 8.0 Hz, 1H), 7.02 (d, J = 8.4 Hz, 1H), 6.94
13
(d, J = 8.4 Hz, 1H), 2.57 (s, 3H), 2.50 (s, 3H); C NMR (100 MHz, DMSO-d6): δ = 149.3, 145.7,
143.7, 142.3, 140.1, 138.8, 137.7, 137.4, 134.6, 133.9, 133.7, 133.4, 132.9, 131.8, 131.4, 131.2, 130.5,
-
129.9, 129.6, 129.2, 129.0, 128.1, 127.4, 127.1, 124.8, 123.6, 120.70 (q, JCF = 320 Hz, CF3SO3 ),
118.4, 114.3, 113.0, 112.7, 111.9, 24.7, 21.3; 19F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-
TOF-positive ionization): calcd for C20H16IN2 ([M-OTf]+): 411.0353, found: 411.0360.
(2-(1H-Benzo[d]imidazol-2-yl)phenyl)(thiophen-2-yl)iodonium triflate (8c)
S
TfO–
+
I
N
N
H
Reaction of [hydroxy(tosyloxy)iodo]arene 7a (0.102 g, 0.2 mmol) with thiophene (0.032 mL, 0.034 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 2 h afforded 0.106 g
1
(96%) of product 8c, isolated as a beige solid: mp 221−222 °C; H NMR (400 MHz, DMSO-d6) δ =
14.03 (s, 1H), 8.43 (d, J = 7.2 Hz, 1H), 8.26 (d, J = 4.4 Hz, 1H), 8.19 (s, 1H), 7.85 (t, J = 7.2 Hz, 1H),
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Page 21 of 46
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7.79 (d, J = 6.4 Hz, 1H), 7.73 (d, J = 6.4 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 7.44 (br.s, 3H), 7.01 (d, J =
5
6
7
8
9
13
8.4 Hz, 1H); C NMR (100 MHz, DMSO-d6): δ = 149.5, 143.5, 139.5, 139.2, 134.4, 133.7, 131.7,
-
130.6, 129.5, 128.6, 126.6, 124.9, 123.8, 120.67 (q, JCF = 320 Hz, CF3SO3 ), 118.0, 116.9, 112.8,
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102.2; F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-TOF-positive ionization): calcd for
C17H12IN2S ([M-OTf]+): 402.9760, found: 402.9754.
(2-(1H-Benzo[d]imidazol-2-yl)phenyl)(4-methoxyphenyl)iodonium triflate (8d)
OMe
TfO–
+
I
N
N
H
Reaction of [hydroxy(tosyloxy)iodo]arene 7a (0.102 g, 0.2 mmol) with 4-anisole (0.040 mL, 0.043 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 3 h afforded 0.099 g
1
(92%) of product 8d (contains 15% of o-isomer), isolated as a beige solid: mp 151−152 °C; H NMR
(500 MHz, DMSO-d6) δ = 8.44 (dd, J = 8.0, 1.5 Hz, 1H), 8.29 (dd, J = 7.5, 1.5 Hz, 1H), 8.26 – 8.21
(m, 2H), 8.19 (dd, J = 7.5, 1.0 Hz, 1H), 7.94 – 7.92 (m, 2H), 7.89 – 7.86 (m, 2H), 7.84 (td, J = 7.5, 1.0
Hz, 1H), 7.76 (br. s, 2H), 7.73 (dd, J = 7.5, 1.0 Hz, 1H), 7.68 – 7.66 (m, 2H), 7.60 (ddd, J = 8.7, 7.4,
1.5 Hz, 1H), 7.54 – 7.51 (m, 2H), 7.43 – 7.41 (m, 2H), 7.30 – 7.24 (m, 2H), 7.05 (dd, J = 8.5, 1.0 Hz,
1H), 3.92 (s, 3H); 13C NMR (125 MHz, DMSO-d6): δ = 162.8, 149.3, 140.1, 139.4, 134.1, 133.4,
-
132.3, 131.1, 131.0, 130.3, 130.2, 128.9, 128.6, 127.0, 126.5, 120.68 (q, JCF = 320 Hz, CF3SO3 ),
118.0, 114.7, 114.4, 104.3, 55.8, 55.2; 19F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-TOF-
positive ionization): calcd for C20H16IN2O ([M-OTf]+): 427.0302, found: 427.0301.
Mesityl(2-(6-nitro-1H-benzo[d]imidazol-2-yl)phenyl)iodonium triflate (8e)
Me
Me
Me
Me
TfO–
N
TfO–
N
+
+
Me
Me
I
I
O2N
N
H
N
H
O2N
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The Journal of Organic Chemistry
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9
Reaction of [hydroxy(tosyloxy)iodo]arene 7b (0.111 g, 0.2 mmol) with mesitylene (0.056 mL, 0.048 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at room temperature during 9 h afforded
0.106 g (92%) of product 8e (mixture of tautomers), isolated as a beige solid: mp 241-242 °C; 1H NMR
(400 MHz, DMSO-d6) δ = 14.47 (s, 1H), 8.62 (s, 1H), 8.51 – 8.44 (m, 1H), 8.26 (t, J = 8.4 Hz, 1H),
7.96 – 7.88 (m, 2H), 7.65 (t, J = 8.0 Hz, 1H), 7.40 (s, 2H), 6.96 (d, J = 8.4 Hz, 1H), 2.55 (s, 6H), 2.43
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(s, 3H); C NMR (100 MHz, DMSO-d6): δ = 154.0, 153.4, 144.5, 144.3, 144.0, 143.6, 143.1, 139.5,
139.1, 137.1, 134.8, 134.7, 134.0, 131.5, 130.3, 130.1, 129.2, 127.1, 126.8, 120.71 (q, JCF = 321 Hz,
-
19
CF3SO3 ), 120.6, 119.9, 119.0, 114.6, 113.2, 112.0, 109.0, 26.1, 20.9; F NMR (376 MHz, DMSO-
d6): δ = -77.8; HRMS (ESI-TOF-positive ionization): calcd for C22H19IN3O2 ([M-OTf]+): 484.0516,
found: 484.0534. The crystal suitable for X-ray was prepared by diffusion of ether to the saturated
solution of 8e in MeOH.
(2-(6-Nitro-1H-benzo[d]imidazol-2-yl)phenyl)(p-tolyl)iodonium triflate (8f)
Me
Me
TfO–
N
TfO–
N
+
+
I
I
O2N
N
H
N
H
O2N
Reaction of [hydroxy(tosyloxy)iodo]arene 7b (0.111 g, 0.2 mmol) with toluene (0.064 mL, 0.055 g,
0.6 mmol) in 1.5 mL TFE (HFIP) according to the general procedure at 50 °C during 48 h (9 h with
HFIP) afforded 0.096 g (79%) [or 0.106 g (88%) with HFIP] of product 8f (mixture of tautomers,
contains 20% of o-isomer), isolated as a beige solid: mp 228−229 °C; 1H NMR (400 MHz, DMSO-d6)
δ = 8.61 (s, 1H), 8.48 (d, J = 7.6 Hz, 1H), 8.37 (d, J = 7.6 Hz, 1H), 8.28 (dd, J = 8.8, 2.0 Hz, 1H), 8.23
(d, J = 8.0 Hz, 2H), 7.93 (d, J = 8.8 Hz, 1H), 7.87 (t, J = 7.2 Hz, 1H), 7.82 – 7.78 (m, 2H), 7.65 (t, J =
7.2 Hz, 1H), 7.55 (d, J = 8.0 Hz, 2H), 7.51 – 7.47 (m, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.99 (d, J = 8.4
13
Hz, 1H), 2.57 (s, 3H), 2.50 (s, 3H); C NMR (100 MHz, DMSO-d6): δ = 154.6, 143.8, 143.4, 142.3,
138.8, 137.3, 134.0, 132.9, 131.8, 131.2, 130.7, 129.9, 129.7, 127.3, 122.3, 120.91 (q, JCF = 322 Hz,
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Page 23 of 46
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CF3SO3 ), 119.1, 115.9, 115.6, 114.8, 113.5, 111.7, 24.7, 21.2; 19F NMR (376 MHz, DMSO-d6): δ = -
77.8; HRMS (ESI-TOF-positive ionization): calcd for C20H15IN3O2 ([M-OTf]+): 456.0203, found:
456.0205.
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(2-(6-Nitro-1H-benzo[d]imidazol-2-yl)phenyl)(thiophen-2-yl)iodonium triflate (8g)
S
S
TfO–
N
TfO–
N
+
+
I
I
O2N
N
H
N
H
O2N
Reaction of [hydroxy(tosyloxy)iodo]arene 7b (0.111 g, 0.2 mmol) with thiophene (0.032 mL, 0.034 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 3 h afforded 0.103 g
1
(86%) of product 8g (mixture of tautomers), isolated as a beige solid: mp 229-230 °C; H NMR (400
MHz, DMSO-d6) δ = 8.63 (br. s, 1H), 8.48 (d, J = 7.2 Hz, 1H), 8.29 (d, J = 6.4 Hz, 2H), 8.24 (d, J =
3.2 Hz, 1H), 7.95 – 7.89 (m, 2H), 7.72 (t, J = 7.2 Hz, 1H), 7.48 – 7.46 (m, 1H), 7.08 (d, J = 8.0 Hz,
1H); 13C NMR (125 MHz, DMSO-d6): δ = 154.0, 153.4, 144.1, 143.9, 143.7, 140.1, 138.9, 138.7,
-
134.6, 133.9, 131.5, 130.7, 129.7, 129.5, 129.3, 125.9, 120.67 (q, JCF = 321 Hz, CF3SO3 ), 120.1,
19
119.2, 118.6, 117.2, 114.2, 113.4, 109.2, 100.9, 100.7; F NMR (376 MHz, DMSO-d6): δ = -77.8;
HRMS (ESI-TOF-positive ionization): calcd for C17H11IN3O2S ([M-OTf]+): 447.9611, found:
447.9622.
(2-(6-Nitro-1H-benzo[d]imidazol-2-yl)phenyl)(4-methoxyphenyl)iodonium triflate (8h)
OMe
OMe
TfO–
N
TfO–
N
+
+
I
I
O2N
N
H
N
H
O2N
Reaction of [hydroxy(tosyloxy)iodo]arene 7b (0.111 g, 0.2 mmol) with 4-anisole (0.040 mL, 0.043 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 3 h afforded 0.102 g
(82%) of product 8h (mixture of tautomers, contains 15% of o-isomer), isolated as a beige solid: mp
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191−192 °C; 1H NMR (400 MHz, DMSO-d6) δ = 14.08 (d, J = 9.2 Hz, 1H), 8.43 (d, J = 7.6 Hz, 1H),
8.30 (dd, J = 8.0, 1.6 Hz, 1H), 8.24 (d, J = 8.8 Hz, 2H), 7.91 – 7.89 (m, 1H), 7.87 – 7.80 (m, 3H), 7.64
– 7.60 (m, 1H), 7.53 – 7.48 (m, 2H), 7.45 – 7.44 (m, 1H), 7.27 (d, J = 9.2 Hz, 2H), 7.11 (d, J = 8.0 Hz,
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1H), 7.06 (d, J = 8.0, 1H), 3.92 (s, 3H); C NMR (100 MHz, DMSO-d6): δ = 162.9, 139.5, 133.7,
-
131.2, 130.5, 129.1, 128.1, 126.8, 123.9, 123.87 (q, JCF = 322 Hz, CF3SO3 ), 118.0, 114.7, 104.0, 55.8;
19F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-TOF-positive ionization): calcd for
C20H15IN3O3 ([M-OTf]+): 472.0158, found: 472.0149.
Mesityl(2-(6-methyl-1H-benzo[d]imidazol-2-yl)phenyl)iodonium triflate (8i)
Me
Me
Me
Me
TfO–
N
TfO–
N
+
+
Me
Me
I
I
Me
N
H
N
H
Me
Reaction of [hydroxy(tosyloxy)iodo]arene 7c (0.104 g, 0.2 mmol) with mesitylene (0.056 mL, 0.048 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at room temperature during 8 h afforded
1
0.113 g (94%) of product 8i (mixture of tautomers), isolated as a beige solid: mp 221−222 °C; H
NMR (400 MHz, DMSO-d6) δ = 13.78 and 13.73 (2s, 1H), 8.44 (d, J = 7.6 Hz, 1H), 7.85 (t, J = 7.2 Hz,
1H), 7.67 – 7.51 (m, 3H), 7.31 (s, 2H), 7.26 and 7.22 (2d, J = 8.4 Hz, 1H), 6.91 (dd, J = 8.4, 2.4 Hz,
1H), 2.52 (s, 6H), 2.49 (s, 3H), 2.42 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ = 149.1, 148.8, 144.0,
143.0, 140.4, 138.3, 134.9, 134.5, 133.6, 133.5, 132.8, 132.7, 131.4, 130.0, 129.2, 128.8, 127.8, 126.3,
-
125.1, 121.1, 121.0, 120.70 (q, JCF = 321 Hz, CF3SO3 ), 118.0, 112.1, 111.4, 111.4, 26.0, 21.4, 21.3,
20.9; 19F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-TOF-positive ionization): calcd for
C23H22IN2 ([M-OTf]+): 453.0822, found: 453.0824.
(2-(6-Methyl-1H-benzo[d]imidazol-2-yl)phenyl)(p-tolyl)iodonium triflate (8j)
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Me
Me
TfO–
N
TfO–
+
+
I
I
Me
N
N
H
N
H
Me
10
11
12
13
14
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60
Reaction of [hydroxy(tosyloxy)iodo]arene 7c (0.104 g, 0.2 mmol) with toluene (0.064 mL, 0.055 g, 0.6
mmol) in 1.5 mL TFE (HFIP) according to the general procedure at 50 °C during 48 h (9 h with HFIP)
afforded 0.094 g (82%) [or 0.104 g (91%) with HFIP] of product 8j (mixture of tautomers, contains
5% of o-isomer), isolated as a beige solid: mp 223−224 °C; 1H NMR (500 MHz, DMSO-d6) δ = 13.71
(s, 1H), 8.41 (dd, J = 7.5, 1.0 Hz, 1H), 8.19 (d, J = 8.0 Hz, 2H), 7.82 (t, J = 7.5 Hz, 1H), 7.64 – 7.49
13
(m, 5H), 7.24 (s, 1H), 6.99 (d, J = 8.5 Hz, 1H), 2.49 (s, 6H); C NMR (125 MHz, DMSO-d6): δ =
148.8, 143.7, 138.2, 137.3, 134.8, 134.5, 133.1, 132.8, 131.1, 130.4, 128.7, 128.1, 127.1, 126.2, 125.5,
-
125.1, 120.68 (q, JCF = 321 Hz, CF3SO3 ), 117.8, 114.1, 112.1, 111.9, 24.7, 21.3, 21.2; 19F NMR (376
MHz, DMSO-d6): δ = -77.7; HRMS (ESI-TOF-positive ionization): calcd for C21H18IN2 ([M-OTf]+):
425.0509, found: 425.0504.
(2-(6-Methyl-1H-benzo[d]imidazol-2-yl)phenyl)(thiophen-2-yl)iodonium triflate (8k)
S
S
TfO–
N
TfO–
N
+
+
I
I
Me
N
H
N
H
Me
Reaction of [hydroxy(tosyloxy)iodo]arene 7c (0.104 g, 0.2 mmol) with thiophene (0.032 mL, 0.034 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 2 h afforded 0.103 g
(91%) of product 8k (mixture of tautomers), isolated as a beige solid: mp 220−221 °C; 1H NMR (400
MHz, DMSO-d6) δ = 13.91 (s, 1H), 8.43 (d, J = 7.6 Hz, 1H), 8.26 (d, J = 5.2 Hz, 1H), 8.20 (t, J = 3.2
Hz, 1H), 7.86 (t, J = 7.6 Hz, 1H), 7.69 – 7.60 (m, 2H), 7.56 (s, 1H), 7.51 (s, 1H), 7.45 (t, J = 3.6 Hz,
1H), 7.29 – 7.22 (m, 1H), 7.01 (d, J = 8.0 Hz, 1H), 2.49 (s, 3H); 13C NMR (125 MHz, DMSO-d6): δ =
149.3, 149.1, 143.5, 139.5, 137.4, 134.8, 134.7, 133.6, 133.5, 133.2, 132.5, 131.4, 130.6, 129.5, 128.5,
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126.7, 126.5, 125.4, 120.70 (q, JCF = 320 Hz, CF3SO3 ), 117.6, 117.5, 116.8, 112.4, 112.3, 102.5,
6
7
8
9
19
102.4, 21.4, 21.3; F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-TOF-positive ionization):
calcd for C18H14IN2S ([M-OTf]+): 416.9917, found: 416.9918.
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(4-Methoxyphenyl)(2-(6-methyl-1H-benzo[d]imidazol-2-yl)phenyl)iodonium triflate (8l)
OMe
OMe
TfO–
N
TfO–
N
+
+
I
I
Me
N
H
N
H
Me
Reaction of [hydroxy(tosyloxy)iodo]arene 7c (0.104 g, 0.2 mmol) with 4-anisole (0.040 mL, 0.043 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 3 h afforded 0.105 g
(89%) of product 8l (mixture of tautomers, contains 35% of o-isomer), isolated as a beige solid: mp
1
189−190 °C; H NMR (400 MHz, DMSO-d6) δ = 13.80 (s, 1H), 13.75 (s, 1H), 8.42 (d, J = 7.2 Hz,
1H), 8.24 (d, J = 7.2 Hz, 2H), 8.15 (d, J = 8.0 Hz, 1H), 7.85 – 7.82 (m, 1H), 7.74 (d, J = 8.4 Hz, 1H),
7.68 – 7.46 (m, 4H), 7.46 – 7.39 (m, 2H), 7.28 – 7.22 (m, 3H), 7.03 (d, J = 8.0 Hz, 1H), 3.92 (s, 3H);
13C NMR (100 MHz, DMSO-d6): δ = 162.8, 148.9, 139.6, 139.5, 138.3, 134.9, 134.5, 133.3, 133.2,
-
132.1, 131.1, 130.3, 128.7, 128.5, 125.2, 124.66 (q, JCF = 329 Hz, CF3SO3 ), 118.0, 114.5, 112.1,
104.4, 55.8, 21.4, 21.2; 19F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-TOF-positive
ionization): calcd for C21H18IN2O ([M-OTf]+): 441.0458, found: 441.0468.
(2-(6-Chloro-1H-benzo[d]imidazol-2-yl)phenyl)(mesityl)iodonium triflate (8m)
Me
Me
Me
Me
TfO–
N
TfO–
N
+
+
Me
Me
I
I
Cl
N
H
N
H
Cl
Reaction of [hydroxy(tosyloxy)iodo]arene 7d (0.109 g, 0.2 mmol) with mesitylene (0.056 mL, 0.048 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at room temperature during 8 h afforded
0.105 g (84%) of product 8m (mixture of tautomers), isolated as a beige solid: mp 222−223 °C; 1H
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NMR (400 MHz, DMSO-d6) δ = 14.05 (d, J = 12.0 Hz, 1H), 8.46 (d, J = 7.6 Hz, 1H), 7.87 (td, J = 7.6,
0.4 Hz, 1H), 7.80 (br. s, 2H), 7.59 (ddd, J = 8.6, 7.5, 1.4 Hz, 1H), 7.44 (br. s, 1H), 7.38 (s, 2H), 6.93 (d,
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J = 8.0 Hz, 1H), 2.53 (s, 6H), 2.43 (s, 3H); C NMR (100 MHz, DMSO-d6): δ = 150.8, 150.6, 144.1,
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143.0, 141.0, 139.0, 135.4, 134.1, 133.5, 131.5, 130.0, 129.7, 129.0, 128.2, 127.5, 124.8, 123.9, 120.9,
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120.72 (q, JCF = 321 Hz, CF3SO3 ), 119.9, 117.9, 114.1, 112.3, 111.7, 26.0, 20.9; 19F NMR (376 MHz,
DMSO-d6): δ = -77.8; HRMS (ESI-TOF-positive ionization): calcd for C22H19ClIN2 ([M-OTf]+):
473.0276, found: 473.0274. The crystal suitable for X-ray was prepared by diffusion of ether to the
saturated solution of 8m in MeOH.
(2-(6-Chloro-1H-benzo[d]imidazol-2-yl)phenyl)(p-tolyl)iodonium triflate (8n)
Me
Me
TfO–
N
TfO–
N
+
+
I
I
Cl
N
H
N
H
Cl
Reaction of [hydroxy(tosyloxy)iodo]arene 7d (0.109 g, 0.2 mmol) with toluene (0.064 mL, 0.055 g,
0.6 mmol) in 1.5 mL TFE (HFIP) according to the general procedure at 50 °C during 48 h (9 h with
HFIP) afforded 0.096 g (81%) or 0.111 g (93%) with HFIP of product 8n (mixture of tautomers,
contains 20% of o-isomer), isolated as a beige solid: mp 158-159 °C; 1H NMR (400 MHz, DMSO-d6)
δ = 14.09 (s, 1H), 8.47 (s, 1H), 8.43 (dd, J = 8.0, 1.2 Hz, 1H), 8.35 (d, J = 7.2 Hz, 1H), 8.21 (d, J = 8.0
Hz, 2H), 7.88 – 7.76 (m, 4H), 7.63 – 7.59 (m, 1H), 7.54 (d, J = 8.0 Hz, 2H), 7.50 – 7.48 (m, 1H), 7.44
(dd, J = 8.4, 1.2 Hz, 1H), 7.04 (d, J = 7.6 Hz, 1H), 6.95 (d, J = 7.6 Hz, 1H), 2.57 (s, 3H), 2.50 (s, 3H);
13C NMR (100 MHz, DMSO-d6): δ = 150,7, 148.8, 143.8, 142.3, 138.8, 137.3, 133.9, 133.6, 132.9,
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131.8, 131.3, 131.2, 130.0, 129.6, 129.4, 129.2, 127.2, 126.9, 120.67 (q, JCF = 321 Hz, CF3SO3 ),
119.9, 114.4, 113.0, 111.6, 111.1, 24.7, 21.2; 19F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-
TOF-positive ionization): calcd for C20H15ClIN2 ([M-OTf]+): 444.9963, found: 444.9956.
(2-(6-Chloro-1H-benzo[d]imidazol-2-yl)phenyl)(thiophen-2-yl)iodonium triflate (8o)
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S
S
TfO–
N
TfO–
+
+
I
I
Cl
N
8
9
N
H
N
H
Cl
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Reaction of [hydroxy(tosyloxy)iodo]arene 7d (0.109 g, 0.2 mmol) with thiophene (0.032 mL, 0.034 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 2 h afforded 0.104 g
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(89%) of product 8o (mixture of tautomers), isolated as a beige solid: mp 238−239 °C; H NMR (400
MHz, DMSO-d6) δ = 8.43 (t, J = 6.4 Hz, 1H), 8.27 (d, J = 5.2 Hz, 1H), 8.21 (s, 1H), 7.87 (t, J = 7.6
Hz, 1H), 7.82 – 7.74 (m, 2H), 7.67 (t, J = 7.6 Hz, 1H), 7.47 – 7.43 (m, 2H), 7.03 (d, J = 8.4 Hz, 1H);
13C NMR (100 MHz, DMSO-d6): δ = 151.0, 150.8, 143.8, 140.2, 139.8, 138.2, 135.3, 134.1, 134.0,
133.5, 131.5, 130.7, 129.6, 129.2, 128.9, 128.0, 126.5, 126.4, 125.1, 124.3, 120.72 (q, JCF = 320 Hz,
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CF3SO3 ), 119.4, 117.5, 117.0, 114.3, 112.6, 101.7; 19F NMR (376 MHz, DMSO-d6): δ = -77.8;
HRMS (ESI-TOF-positive ionization): calcd for C17H11ClIN2S ([M-OTf]+): 436.9371, found:
436.9373.
(2-(6-Chloro-1H-benzo[d]imidazol-2-yl)phenyl)(4-methoxyphenyl)iodonium triflate (8p)
OMe
OMe
TfO–
N
TfO–
N
+
+
I
I
Cl
N
H
N
H
Cl
Reaction of [hydroxy(tosyloxy)iodo]arene 7d (0.109 g, 0.2 mmol) with 4-anisole (0.040 mL, 0.043 g,
0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 3 h afforded 0.099 g
(81%) of product 8p (mixture of tautomers, contains 13% of o-isomer), isolated as a beige solid: mp
191−192 °C; 1H NMR (400 MHz, DMSO-d6) δ = 14.06 (d, J = 9.2 Hz, 1H), 8.43 (d, J = 7.6 Hz, 1H),
8.29 (dd, J = 8.0, 1.6 Hz, 1H), 8.24 (d, J = 8.8 Hz, 2H), 7.90 (d, J = 7.6 Hz, 1H), 7.87 – 7.80 (m, 3H),
7.64 – 7.59 (m, 1H), 7.53 – 7.48 (m, 2H), 7.45 (m, 1H), 7.27 (d, J = 9.2 Hz, 2H), 7.11 (d, J = 8.0 Hz,
1H), 7.06 (d, J = 8.0 Hz, 1H), 3.92 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ = 162.9, 150.6, 139.5,
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138.4, 133.7, 132.2, 131.2, 130.5, 129.1, 128.1, 126.8, 124.9, 123.9, 120.67 (q, JCF = 320 Hz, CF3SO3
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), 119.7, 114.7, 114.1, 112.3, 104.0, 55.8; F NMR (376 MHz, DMSO-d6): δ = -77.8; HRMS (ESI-
TOF-positive ionization): calcd for C20H15ClIN2O ([M-OTf]+): 460.9912, found: 460.9914.
(2-(6-Chloro-1H-benzo[d]imidazol-2-yl)phenyl)(2,4,6-trimethoxyphenyl)iodonium triflate (8q)
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OMe
OMe
MeO
MeO
TfO–
N
TfO–
N
+
+
I
I
OMe
OMe
Cl
N
H
N
H
Cl
Reaction of [hydroxy(tosyloxy)iodo]arene 7d (0.109 g, 0.2 mmol) with 1,3,5-trimethoxybenzene
(0.067 g, 0.4 mmol) in 1.5 mL TFE according to the general procedure at 0-5 °C during 2 h afforded
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0.129 g (96%) of product 8q (mixture of tautomers), isolated as a beige solid: mp 236−237 °C; H
NMR (400 MHz, DMSO-d6) δ = 14.10 (s, 1H), 8.44 (t, J = 6.4 Hz, 1H), 7.87 – 7.73 (m, 3H), 7.61 (t, J
= 7.6 Hz, 1H), 7.46 – 7.40 (m, 1H), 7.10 (d, J = 8.0 Hz, 1H), 6.63 (s, 2H), 3.98 (s, 4H), 3.89 (s, 7H);
13C NMR (100 MHz, DMSO-d6): δ = 167.3, 161.0, 150.8, 150.6, 140.7, 138.7, 135.3, 134.0, 133.9,
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133.4, 131.3, 129.4, 129.0, 128.2, 127.7, 127.0, 124.9, 124.0, 122.3, 120.71 (q, JCF = 320 Hz, CF3SO3
), 119.7, 117.7, 114.1, 112.6, 112.4, 92.4, 85.7, 57.4, 56.4; 19F NMR (376 MHz, DMSO-d6): δ = -77.8;
HRMS (ESI-TOF-positive ionization): calcd for C22H19ClIN2O3 ([M-OTf]+): 521.0123, found:
521.0117.
(2-(5,6-Difluoro-1H-benzo[d]imidazol-2-yl)phenyl)(mesityl)iodonium triflate (8r)
Me
Me
TfO–
+
Me
I
F
N
N
H
F
Reaction of [hydroxy(tosyloxy)iodo]arene 7f (0.109 g, 0.2 mmol) with mesitylene (0.056 mL, 0.048 g,
0.4 mmol) in 1.5 mL HFIP according to the general procedure at room temperature during 8 h afforded
0.102 g (82%) of product 8r, isolated as a beige solid: mp 166-167 °C; 1H NMR (400 MHz, DMSO-d6)
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