Direct Arylations of Heteroarenes with Benzenesulfonyl Chlorides Using Pd/C Catalyst

Article abstract of DOI:10.1002/ejoc.201901561

The reactivity of heteroaromatics in direct arylation with benzenesulfonyl chlorides using 10 % Pd/C as catalyst was explored. With (benzo)thiophenes, (benzo)furans, pyrroles and selenophenes, high yields in arylated heteroarenes were obtained. These arylations were performed using only 5 mol-% Pd/C and Li₂CO₃ as inexpensive base. The regioselectivities are similar to those observed with homogeneous palladium catalysts. Better yields were obtained with electron-deficient benzenesulfonyl chlorides than with the electron-rich ones. Notably, useful substituents such as bromo or iodo on the benzenesulfonyl chloride were tolerated, as no cleavage of the C–Br or C–I bonds was observed under these conditions. The use of Pd/C presents several advantages compared to the previously employed homogeneous palladium catalysts, as it can be easily removed by filtration at the end of the reaction. The major side-products of the reaction are HBr associated to Li₂CO₃. Therefore, this new protocol affords a very attractive synthetic scheme in terms of cost, simplicity and low environmental impact for the access to arylated heteroaromatics.

Full text of DOI:10.1002/ejoc.201901561

DOI: 10.1002/ejoc.201901561
Full Paper
Direct Arylation
Direct Arylations of Heteroarenes with Benzenesulfonyl
Chlorides Using Pd/C Catalyst
Shuxin Mao,[a] Xinzhe Shi,[a] Jean-François Soulé,*[a] and Henri Doucet*[a]
Abstract: The reactivity of heteroaromatics in direct arylation onyl chloride were tolerated, as no cleavage of the C–Br or C–I
with benzenesulfonyl chlorides using 10 % Pd/C as catalyst was bonds was observed under these conditions. The use of Pd/C
explored. With (benzo)thiophenes, (benzo)furans, pyrroles and presents several advantages compared to the previously em-
selenophenes, high yields in arylated heteroarenes were ob- ployed homogeneous palladium catalysts, as it can be easily
tained. These arylations were performed using only 5 mol-% removed by filtration at the end of the reaction. The major side-
Pd/C and Li2CO3 as inexpensive base. The regioselectivities are products of the reaction are HBr associated to Li2CO3. Therefore,
similar to those observed with homogeneous palladium cata- this new protocol affords a very attractive synthetic scheme in
lysts. Better yields were obtained with electron-deficient benz- terms of cost, simplicity and low environmental impact for the
enesulfonyl chlorides than with the electron-rich ones. Notably, access to arylated heteroaromatics.
useful substituents such as bromo or iodo on the benzenesulf-
Introduction
Many drugs contain an aryl substituent on a 5-membered ring
heteroarene (Figure 1). For example, Atorvastatin which is used
to prevent cardiovascular diseases is one of the most prescribed
drugs. Canagliflozin is a medication used to treat type 2 diabe-
tes. Saprisartan is an AT1 receptor antagonist. Raloxifene is a
medication used to prevent and treat osteoporosis, and Lapa-
tinib is an orally active drug used against breast cancer and
other solid tumors. In addition, aryl-substituted heteroarenes
are ubiquitous units in organic material science.[1] Therefore,
the development of new procedures using easily accessible and
easy to handle inexpensive reagents that allow access to such
structures in a few steps is of great interest to pharmacochem-
ists as well as to researchers working in the field of organic
materials.
The Pd-catalyzed reactions such as Stille, Suzuki and Negishi
cross-couplings are very effective tools for the access to aryl-
substituted heteroarenes. These coupling reactions tolerate
many useful functional groups and high yields in target prod-
ucts are often obtained. However, one of the major drawback
of such couplings is that they require the preliminary synthesis
of organometallic or boron derivatives.[2] In 1985, Ohta et al.
described the Pd-catalyzed arylation of heteroarenes via the
cleavage of C–H bonds using aryl bromides as aryl sources[3]
Since this seminal report, the so-called “direct arylations” of
Figure 1. Representative examples of drugs containing an aryl-substituted
heteroarene.
heteroarenes using Pd-catalysis was demonstrated to be a very
[a] Univ Rennes, CNRS, ISCR-UMR 6226
effective method for the preparation of arylated heteroarenes
(Scheme 1, a).[4–7] For these arylations, in addition to aryl hal-
35000 Rennes, France
E-mail: jean-francois.soule@univ-rennes1.fr
henri.doucet@univ-rennes1.fr
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201901561.
ides, a variety of aryl sources such as benzenesulfonyl chlorides
can be employed. The use of benzenesulfonyl chlorides is very
attractive as in some cases, the regioselectivity of the arylation
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is modified and as they allow the synthesis of molecules con- as the solvent afforded the desired coupling product 1 in lower
taining several halo-substituents including iodo, due to the yields of 68 % and 15 %, respectively. We also studied the possi-
C-halo bond tolerance of the reactions performed with these bility of recycling the Pd/C catalyst. The Pd/C recovered by filtra-
substrates.[8–10] To the best of our knowledge, in all cases the tion through filter paper was used for a second run which af-
Pd-catalyzed direct arylations of heteroarenes by benzenesulf- forded 1 in a lower yield of 44 %.
onyl chlorides were performed using homogeneous catalysts
(Scheme 1, b).[8]
Scheme 2. Pd/C-catalyzed coupling of 2-methylthiophene with benzenesulf-
onyl chlorides.
The mechanism of the direct arylations of heteroarenes us-
ing Pd/C catalyst has not yet been elucidated. In 2003 Conlon
et al. studied the mechanism of the Suzuki–Miyaura reaction
using Pd/C.[18a] They suggested that this reaction might have
a homogeneous component due to the formation of soluble
palladium-species coming from the desorption of the palladium
from Pd/C to produce soluble PdII species. Such desorption may
occur after the oxidative addition of the aryl halide on the
Pd/C surface. The direct arylation of heteroarenes might pro-
ceed via a similar mechanism.
Scheme 1. Pd-catalyzed direct arylations of heteroarenes.
Pd/C catalyst displays several advantages over homogeneous
palladium catalysts:[11] 1) it is easy to handle because it is not
sensitive to air or moisture, 2) it is readily available on a large
scale and at an affordable cost, 3) it can be removed by simple
filtration, 4) recycling of the recovered Pd/C residues is possible
in some cases or they can be reconditioned. However, to date
the Pd-catalyzed direct arylation of heteroarenes using Pd/C is
limited to the reactions with aryl halides.[12–15] A few other het-
erogeneous Pd-catalysts such as Pd(OH)2, zeolites or nanoparti-
cles have also been successfully employed for the direct aryl-
ation of heteroaromatics with aryl halides.[16,17]
In order to better understand the mechanism of the coupling
using benzenesulfonyl chlorides with Pd/C, the mercury poison-
ing test was applied to this reaction. When a drop of Hg was
added to the reaction mixture, no formation of product 1 was
1
detected by GC/MS, and H NMR analysis of the crude mixture
(Scheme 2). Such reaction inhibition is generally observed when
the catalytic cycle involves heterogeneous species including
colloidal Pd0.[19a] However, in a few cases, Hg0 interaction with
soluble molecular Pd complexes was also found to inhibit cata-
lytic reactions.[19b,19c]
As the efficacy of the Pd/C catalyst in direct heteroarene aryl-
ations by benzenesulfonyl chlorides has not yet been described,
we investigated its potential using a set of heteroarenes
(Scheme 1, bottom).
The kinetics of the formation of product 1 using both Pd/C
and Pd(OAc)2 catalysts was measured (Scheme 3, a). With Pd/C,
an induction period was observed with <1 % yield in 1 after 15
Results and Discussion
Using reaction conditions similar to those employed with ho- minutes. Conversely, with Pd(OAc)2 after 15 minutes 4 % of 1
mogeneous palladium catalyst,[9] we first studied the reactivity was obtained. At 4 h the yields in 1 with Pd/C and Pd(OAc)2
of 2-methylthiophene (1.5 equiv.) using 4-(trifluoromethyl)- were 17 % and 33 %, respectively; whereas after 16 h, similar
benzenesulfonyl chloride (1 equiv.) as the aryl source in the yield in 1 were obtained with these two catalysts. The induction
presence of 5 mol-% Pd/C (10 %) (Scheme 2). With Li2CO3 as the period for the Pd/C catalyzed reaction might come from a slow
base at 150 °C, the C4-arylated thiophene 1 was regioselectively leaching to produce catalytically active palladium clusters or
obtained in 79 % yield. It should be noted that this regioselecti- nanoparticles. In order to confirm the formation of soluble clus-
vity (C4-arylation) is different from the regioselectivity observed ters or nanoparticles, a hot filtration test[20] was performed
with aryl bromide and Pd/C (C5-arylations). This difference of (Scheme 3, b). The yield in 1 with Pd/C at 150 °C after 4 h was
regioselectivity for the arylation of thiophenes using benzene- 13 %; then, the reaction mixture was filtered through a pad of
sulfonyl chlorides or aryl bromides had already been observed Celite, and 1 equiv. of Li2CO3 was added to the solution which
with homogeneous Pd-catalysts.[9] The use of a lower reaction was heated again at 150 °C during 4 h. The filtrate was catalyti-
temperature of 130 °C, or the use of cyclopentyl methyl ether cally active, as after 8 h the reaction progressed to 21 % yield.
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This result supports the formation of catalytically active soluble
clusters or nanoparticles from Pd/C.[21]
Under the same reaction conditions using Pd/C, the direct
arylation of benzothiophene with benzenesulfonyl chlorides
regioselectively gave the C3-arylated benzothiophenes
(Scheme 5). Again, the use of benzenesulfonyl chlorides as the
aryl source instead of aryl bromides modifies the regioselecti-
vity of the arylation. In the presence of aryl bromides and
Pd/C, regioselective C2-arylations of benzothiophene had been
previously observed.[9] The reaction tolerates a range of substit-
uents on the benzenesulfonyl chloride. However, again higher
yields in desired coupling products were obtained in the pres-
ence of electron-withdrawing groups such as trifluoromethyl or
chloro than with 4-methoxybenzenesulfonyl chloride. From 4-
bromo- and even 4-iodo-benzenesulfonyl chlorides, the halo-
containing 3-arylbenzothiophenes 13 and 14 were obtained in
moderate yields.
Scheme 3. Kinetics of the direct arylation of 2-methylthiophene with 4-(tri-
fluoromethyl)benzenesulfonyl chloride using Pd/C or Pd(OAc)2 catalysts and
hot filtration test.
Then, a set of benzenesulfonyl chlorides was treated with 2-
methylthiophene using Pd/C (Scheme 4). From benzenesulfonyl
chlorides bearing chloro or fluoro para-substituents, the desired
products 2 and 3 were obtained in 62 % and 77 % yield, respec-
tively. By contrast, the reaction of electron-rich 4-methoxy-
benzenesulfonyl chloride gave the product 5 in only 21 % yield,
due to a low conversion of this benzenesulfonyl chloride. As
the use of benzenesulfonyl chlorides in Pd-catalyzed direct aryl-
ations tolerates bromo-substituents,[8] the behavior of 3-bromo-
and 4-bromo-benzenesulfonyl chlorides was also investigated.
With 4-bromobenzenesulfonyl chloride, a moderate yield in the
target product 6 was obtained due to a poor conversion. Con-
versely, the use of 3-bromobenzenesulfonyl chloride afforded
the product 7 in 79 % yield. In both cases, no cleavage of the
C–Br bond was observed.
Scheme 5. Pd/C-catalyzed coupling of benzothiophene with benzenesulfonyl
chlorides.
The reactivity of Menthofuran, which is a natural compound
found in mint oil, using Pd/C was then investigated (Scheme 6).
The influence of nitro and bromo para-substituents on the
benzenesulfonyl chloride was examined, and both reactions
produced the expected C5-arylated Menthofuran derivatives 15
and 16 in high yields.
Scheme 6. Pd/C-catalyzed coupling of menthofuran with benzenesulfonyl
chlorides.
The regioselective Pd-catalyzed direct arylation of benzo-
furan with aryl halides is a challenging reaction. Such couplings
generally led to mixtures of C2- and C3-arylation products to-
gether with C2,C3-diarylation products, as C2- and C3-positions
of benzofuran display quite similar reactivity.[22] We have re-
ported a few years ago that the use of benzenesulfonyl chlor-
ides instead of aryl halides using the homogeneous catalyst
PdCl2(MeCN)2 allows to control the regioselectivity of the Pd-
catalyzed arylation of benzofurans in favor of C2-position.[22]
When Pd/C was used for the direct arylation of benzofuran with
benzenesulfonyl chlorides, the C2-arylated benzofurans were
Scheme 4. Pd/C-catalyzed coupling of 2-methylthiophene with benzenesulf-
onyl chlorides.
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also regioselectively produced (Scheme 7). At 150 °C after 16 h,
the 2-arylbenzofurans 17–20 were obtained in 57–73 % yields,
from benzenesulfonyl chlorides bearing nitro, trifluoromethyl,
chloro or fluoro para-substituents. Similar yields in products 21
and 22 were obtained from benzenesulfonyl chloride and 4-
methoxybenzenesulfonyl chloride. Notably, from 4-bromo-
benzenesulfonyl chloride, the bromo-substituted 2-arylbenzo-
furan 23 was isolated in 81 % yield.
Scheme 9. Pd/C-catalyzed coupling of selenophene with benzenesulfonyl
chlorides.
Conclusion
Pd/C catalyst was successfully employed to promote the direct
arylation of a range of heteroaromatics using benzenesulfonyl
chlorides as the aryl source. To the best of our knowledge these
are the first examples of desulfitative direct arylations of hetero-
aromatics using a heterogeneous pre-catalyst. These couplings
likely proceed via the formation of homogeneous catalytically
active soluble clusters or nanoparticles from Pd/C. Good to high
yields in arylated heteroaromatics were obtained using a variety
of benzenesulfonyl chlorides. With (benzo)thiophenes and se-
lenophene, the arylation occurred at ꢀ-positions; whereas, with
(benzo)furans and pyrroles α-arylated compounds were ob-
tained. These regioselectivities are similar to those observed
with the homogeneous palladium catalysts Pd(OAc)2 or
PdCl2(MeCN)2 when benzenesulfonyl chlorides were employed
as the aryl sources. This protocol is attractive as 1) Pd/C can be
easily removed by simple filtration, 2) the catalyst, base and
reactants are air-stable and easily available, 3) the reaction tol-
erates useful functional groups such as nitro, trifluoromethyl,
methoxy or even bromo and iodo substituents. For these rea-
sons, this new procedure provides an economically viable and
environmentally very attractive access to arylated heteroaro-
matics.
Scheme 7. Pd/C-catalyzed coupling of benzofuran with benzenesulfonyl
chlorides.
Then, the reactivity of pyrrole derivatives with benzenesulf-
onyl chlorides using Pd/C was examined (Scheme 8). For these
reactions, an excess (3 equiv.) of pyrrole derivative was em-
ployed in order to avoid the formation of 2,5-diarylated pyrrole
derivatives. From 1-methylpyrrole and 4-nitro-, 4-methoxy- and
3-bromo-benzenesulfonyl chlorides, the C2-arylated pyrroles
24–26 were obtained in 71–92 % yields. The reaction also toler-
ated benzyl or fluorobenzene substituents on the nitrogen
atom of pyrrole, providing the products 27 and 28 in good
yields. Under these conditions, no debenzylation was observed.
Experimental Section
1,4-Dioxane (99 %) and Li2CO3 (99 %) were purchased from Fischer.
10 % Pd/C was purchased from Aldrich (Reference 205699 which is
expect to conform to the following: approximately 90 % <60 μm
and 10 % <5 μm with an average particle size of 15 μm). These
compounds were not purified before use.
Scheme 8. Pd/C-catalyzed coupling of pyrrole derivatives with benzenesulf-
onyl chlorides.
Typical Experiment for Coupling Reactions: The reaction of the
benzenesulfonyl chloride (1 mmol), heteroaromatic (1.5 or 3 mmol)
(see schemes ) and Li2CO3 (0.222 g, 3 mmol) in the presence of
10 % Pd/C (0.055 g, 5 mol-%) in 1,4-dioxane under argon at 150 °C
during 16 h, affords the corresponding product after cooling, evap-
oration of the solvent and filtration through silica gel (pentane/
ether).
2-Methyl-4-[4-(trifluoromethyl)phenyl]thiophene (1):[9] 4-(Tri-
fluoromethyl)benzenesulfonyl chloride (0.245 g, 1 mmol) and 2-
methylthiophene (0.147 g, 1.5 mmol) affords 1 in 79 % (0.191 g)
yield. 1H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 8.3 Hz, 2H), 7.62
(d, J = 8.3 Hz, 2H), 7.28 (d, J = 1.4 Hz, 1H), 7.07 (d, J = 1.4 Hz, 1H),
2.54 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 141.2, 140.5, 139.4,
In the presence of aryl halides, the Pd-catalyzed direct aryl-
ation of selenophene proceed at C2-position;[18] whereas with
benzenesulfonyl chlorides using the homogeneous catalyst
Pd(OAc)2, C3-arylated selenophenes had been obtained.[19] We
observed that using Pd/C and benzenesulfonyl chlorides, the
arylation of selenophene also occurred regioselectively at C3-
position of selenophene (Scheme 9). Nitro and bromo para-
substituents on the benzenesulfonyl chloride were successfully
employed affording the products 29 and 30 in 56 % and 70 %
yield, respectively. A 4-iodo substituent on the benzenesulfonyl
chloride was also tolerated giving rise to the 3-arylselenophene
31 in 77 % yield.
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128.6 (q, J = 32.6 Hz), 126.5, 125.7 (q, J = 3.2 Hz), 124.3, 124.0 (q,
CDCl3): δ = 7.97–7.90 (m, 1H), 7.90–7.83 (m, 1H), 7.50 (d, J = 8.3 Hz,
J = 271.6 Hz), 119.6, 15.4. LRMS calcd. for M+ C12H9F3S 242, found 2H), 7.46 (d, J = 8.3 Hz, 2H), 7.43–7.37 (m, 3H). 13C NMR (100 MHz,
242.
CDCl3): δ = 140.7, 137.6, 136.8, 134.4, 133.5, 129.9, 128.9, 124.5,
124.4, 123.7, 123.0, 122.6. LRMS calcd. for M+ C14H9ClS 244, found
244.
4-(4-Chlorophenyl)-2-methylthiophene (2):[9] 4-Chlorobenzene-
sulfonyl chloride (0.211 g, 1 mmol) and 2-methylthiophene (0.147 g,
1.5 mmol) affords 2 in 62 % (0.129 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 7.50 (d, J = 8.3 Hz, 2H), 7.37 (d, J = 8.3 Hz, 2H), 7.20 (d,
J = 1.4 Hz, 1H), 7.04 (d, J = 1.4 Hz, 1H), 2.55 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ = 140.9, 140.8, 134.6, 132.7, 128.8, 127.4, 124.4,
118.3, 15.4. LRMS calcd. for M+ C11H9ClS 208, found 208.
3-(4-Fluorophenyl)benzo[b]thiophene (10):[24] 4-Fluorobenzene-
sulfonyl chloride (0.194 g, 1 mmol) and benzothiophene (0.201 g,
1.5 mmol) affords 10 in 60 % (0.137 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 7.97–7.90 (m, 1H), 7.89–7.82 (m, 1H), 7.55 (dd, J = 8.3,
5.6 Hz, 2H), 7.43–7.38 (m, 2H), 7.38 (s, 1H), 7.18 (t, J = 8.3 Hz, 2H).
13C NMR (100 MHz, CDCl3): δ = 162.5 (d, J = 246.6 Hz), 140.8, 138.0,
137.1, 132.2, 130.4 (d, J = 8.1 Hz), 124.6, 124.5, 123.6, 123.1, 122.8,
115.8 (d, J = 21.5 Hz). LRMS calcd. for M+ C14H9FS 228, found 228.
4-(4-Fluorophenyl)-2-methylthiophene (3):[9] 4-Fluorobenzene-
sulfonyl chloride (0.194 g, 1 mmol) and 2-methylthiophene (0.147 g,
1.5 mmol) affords 3 in 77 % (0.148 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 7.50 (dd, J = 8.3, 5.6 Hz, 2H), 7.13 (d, J = 1.4 Hz, 1H),
7.06 (t, J = 8.3 Hz, 2H), 7.00 (d, J = 1.4 Hz, 1H), 2.53 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ = 162.0 (d, J = 245.4 Hz), 141.0, 140.7, 132.3 (d,
J = 3.3 Hz), 127.6 (d, J = 8.1 Hz), 124.5, 117.7, 115.5 (d, J = 21.3 Hz),
15.3. LRMS calcd. for M+ C11H9FS 192, found 192.
3-Phenylbenzo[b]thiophene (11):[9] Benzenesulfonyl chloride
(0.177 g, 1 mmol) and benzothiophene (0.201 g, 1.5 mmol) affords
1
11 in 61 % (0.128 g) yield. H NMR (400 MHz, CDCl3): δ = 7.98–7.90
(m, 2H), 7.61 (d, J = 8.3 Hz, 2H), 7.51 (t, J = 7.9 Hz, 2H), 7.44–7.38
(m, 4H). 13C NMR (100 MHz, CDCl3): δ = 140.7, 138.1, 137.9, 136.0,
128.7, 128.5, 127.5, 124.4, 124.3, 123.4, 122.9. LRMS calcd. for
M+ C14H10S 210, found 210.
2-Methyl-4-phenylthiophene (4):[9] Benzenesulfonyl chloride
(0.177 g, 1 mmol) and 2-methylthiophene (0.147 g, 1.5 mmol) af-
fords 4 in 75 % (0.131 g) yield. H NMR (400 MHz, CDCl3): δ = 7.58
(d, J = 8.3 Hz, 2H), 7.39 (t, J = 7.8 Hz, 2H), 7.29 (t, J = 7.8 Hz, 1H),
7.21 (d, J = 1.4 Hz, 1H), 7.08 (d, J = 1.4 Hz, 1H), 2.55 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ = 142.0, 140.5, 136.1, 128.7, 126.9, 126.2, 124.6,
118.0, 15.5. LRMS calcd. for M+ C11H10S 174, found 174.
1
3-(4-Methoxyphenyl)benzo[b]thiophene (12):[9] 4-Methoxybenz-
enesulfonyl chloride (0.206 g, 1 mmol) and benzothiophene
(0.201 g, 1.5 mmol) affords 12 in 41 % (0.098 g) yield. 1H NMR
(400 MHz, CDCl3): δ = 7.97–7.90 (m, 2H), 7.54 (d, J = 8.3 Hz, 2H),
7.43–7.36 (m, 2H), 7.35 (s, 1H), 7.04 (d, J = 8.3 Hz, 2H), 3.89 (s, 3H).
13C NMR (100 MHz, CDCl3): δ = 159.1, 140.6, 138.1, 137.7, 129.8,
128.5, 124.3, 124.2, 122.9, 122.8, 122.5, 114.1, 55.3. LRMS calcd. for
M+ C15H12OS 240, found 240.
4-(4-Methoxyphenyl)-2-methylthiophene (5):[9] 4-Methoxybenz-
enesulfonyl chloride (0.206 g, 1 mmol) and 2-methylthiophene
(0.147 g, 1.5 mmol) affords 5 in 21 % (0.043 g) yield. 1H NMR
(400 MHz, CDCl3): δ = 7.49 (d, J = 8.1 Hz, 2H), 7.08 (d, J = 1.4 Hz,
1H), 7.00 (d, J = 1.4 Hz, 1H), 6.90 (d, J = 8.1 Hz, 2H), 3.83 (s, 3H),
2.52 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 158.7, 141.7, 140.3,
129.0, 127.3, 124.6, 116.6, 114.1, 55.3, 15.4. LRMS calcd. for M+
C12H12OS 204, found 204.
3-(4-Bromophenyl)benzo[b]thiophene (13):[9] 4-Bromobenzene-
sulfonyl chloride (0.255 g, 1 mmol) and benzothiophene (0.201 g,
1.5 mmol) affords 13 in 45 % (0.130 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 7.97–7.90 (m, 1H), 7.90–7.82 (m, 1H), 7.62 (d, J = 8.3 Hz,
2H), 7.46 (d, J = 8.3 Hz, 2H), 7.43–7.36 (m, 3H). 13C NMR (100 MHz,
CDCl3): δ = 140.7, 137.5, 136.8, 134.8, 131.9, 130.2, 124.6, 124.5,
123.7, 123.0, 122.6, 121.6. LRMS calcd. for M+ C14H9BrS 288, found
288.
4-(4-Bromophenyl)-2-methylthiophene (6):[9] 4-Bromobenzene-
sulfonyl chloride (0.255 g, 1 mmol) and 2-methylthiophene (0.147 g,
1.5 mmol) affords 6 in 38 % (0.096 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 7.49 (d, J = 8.3 Hz, 2H), 7.42 (d, J = 8.3 Hz, 2H), 7.19 (d,
J = 1.4 Hz, 1H), 7.02 (d, J = 1.4 Hz, 1H), 2.53 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ = 140.9, 140.8, 135.0, 131.8, 127.8, 124.3, 120.8,
118.4, 15.4. LRMS calcd. for M+ C11H9BrS 252, found 252.
3-(4-Iodophenyl)benzo[b]thiophene (14): 4-Iodobenzenesulfonyl
chloride (0.302 g, 1 mmol) and benzothiophene (0.201 g, 1.5 mmol)
affords 14 in 54 % (0.181 g) yield. 1H NMR (400 MHz, CDCl3): δ =
7.97–7.89 (m, 1H), 7.89–7.83 (m, 1H), 7.83 (d, J = 8.3 Hz, 2H), 7.45–
7.37 (m, 3H), 7.33 (d, J = 8.3 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ =
140.7, 137.9, 137.5, 136.9, 135.5, 130.5, 124.6, 124.5, 123.8, 123.0,
122.6, 93.1. Anal. Calcd for C14H9IS (336.19): C, 50.02; H, 2.70; found
C, 67.34; H, 3.80.
4-(3-Bromophenyl)-2-methylthiophene (7):[23] 3-Bromobenzene-
sulfonyl chloride (0.255 g, 1 mmol) and 2-methylthiophene (0.147 g,
1.5 mmol) affords 7 in 79 % (0.200 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 7.71 (s, 1H), 7.48 (d, J = 8.3 Hz, 1H), 7.40 (d, J = 8.3 Hz,
1H), 7.39 (t, J = 7.9 Hz, 1H), 7.21 (d, J = 1.4 Hz, 1H), 7.03 (d, J =
1.4 Hz, 1H), 2.53 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 141.1, 140.6,
138.2, 130.4, 129.9, 129.4, 124.9, 124.5, 123.0, 119.1, 15.6. LRMS
calcd. for M+ C11H9BrS 252, found 252.
3,6-Dimethyl-2-(4-nitrophenyl)-4,5,6,7-tetrahydrobenzofuran
(15):[10b] 4-Nitrobenzenesulfonyl chloride (0.221 g, 1 mmol) and
menthofuran (0.225 g, 1.5 mmol) affords 15 in 82 % (0.222 g) yield.
1H NMR (400 MHz, CDCl3): δ = 8.22 (d, J = 8.6 Hz, 2H), 7.71 (d, J =
8.6 Hz, 2H), 2.80–2.60 (m, 1H), 2.50–2.24 (m, 3H), 2.23 (s, 3H), 2.00–
1.80 (m, 2H), 1.50–1.30 (m, 1H), 1.12 (d, J = 7.5 Hz, 3H). 13C NMR
(100 MHz, CDCl3): δ = 152.4, 145.1, 145.0, 138.4, 124.3, 124.2, 121.2,
121.1, 31.6, 31.2, 29.2, 21.5, 120.0, 10.5. LRMS calcd. for M+
C16H17NO3 271, found 271.
3-[4-(Trifluoromethyl)phenyl]benzo[b]thiophene (8):[9] 4-(Tri-
fluoromethyl)benzenesulfonyl chloride (0.245 g, 1 mmol) and
benzothiophene (0.201 g, 1.5 mmol) affords 8 in 71 % (0.197 g)
yield. 1H NMR (400 MHz, CDCl3): δ = 7.98–7.92 (m, 1H), 7.91–7.85
(m, 1H), 7.76 (d, J = 8.3 Hz, 2H), 7.71 (d, J = 8.3 Hz, 2H), 7.48 (s, 1H),
7.45–7.38 (m, 2H). 13C NMR (100 MHz, CDCl3): δ = 140.7, 139.6,
137.4, 136.6, 129.5 (q, J = 32.6 Hz), 128.8, 125.7 (q, J = 4.0 Hz), 124.7,
124.6 (m), 124.1 (q, J = 271.8 Hz), 123.1, 122.5. LRMS calcd. for M+
C15H9F3S 278, found 278.
2-(4-Bromophenyl)-3,6-dimethyl-4,5,6,7-tetrahydrobenzofuran
(16):[10b] 4-Bromobenzenesulfonyl chloride (0.255 g, 1 mmol) and
menthofuran (0.225 g, 1.5 mmol) affords 16 in 84 % (0.256 g) yield.
1H NMR (400 MHz, CDCl3): δ = 7.50 (d, J = 8.6 Hz, 2H), 7.46 (d, J =
8.6 Hz, 2H), 2.80–2.70 (m, 1H), 2.50–2.20 (m, 3H), 2.15 (s, 3H), 2.10–
3-(4-Chlorophenyl)benzo[b]thiophene (9):[9] 4-Chlorobenzene-
sulfonyl chloride (0.211 g, 1 mmol) and benzothiophene (0.201 g, 1.85 (m, 2H), 1.50–1.35 (m, 1H), 1.12 (d, J = 7.5 Hz, 3H). 13C NMR
1.5 mmol) affords 9 in 63 % (0.154 g) yield. 1H NMR (400 MHz,
(100 MHz, CDCl3): δ = 150.1, 145.9, 131.7, 131.5, 126.5, 120.2, 119.7,
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117.0, 31.6, 31.4, 29.8, 21.7, 20.2, 10.1. LRMS calcd. for M+ C16H17BrO
304, found 304.
1-Methyl-2-(4-nitrophenyl)pyrrole (24):[10a] 4-Nitrobenzenesulf-
onyl chloride (0.221 g, 1 mmol) and 1-methylpyrrole (0.243 g,
3 mmol) affords 24 in 92 % (0.186 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 8.26 (d, J = 8.6 Hz, 2H), 7.55 (d, J = 8.6 Hz, 2H), 6.82 (m,
1H), 6.42 (dd, J = 3.4, 1.7 Hz, 1H), 6.25 (t, J = 3.4 Hz, 1H), 3.75 (s,
3H). 13C NMR (100 MHz, CDCl3): δ = 145.9, 139.7, 132.4, 128.1, 126.6,
124.0, 111.5, 108.9, 35.7. LRMS calcd. for M+ C11H10N2O2 202, found
202.
2-(4-Methoxyphenyl)-1-methylpyrrole (25):[10a]. 4-Methoxy-
benzenesulfonyl chloride (0.206 g, 1 mmol) and 1-methylpyrrole
(0.243 g, 3 mmol) affords 25 in 71 % (0.133 g) yield. 1H NMR
(400 MHz, CDCl3): δ = 7.37 (d, J = 8.6 Hz, 2H), 6.99 (d, J = 8.6 Hz,
2H), 6.74 (m, 1H), 6.23 (t, J = 3.4 Hz, 1H), 6.20 (dd, J = 3.4, 1.7 Hz,
1H), 3.89 (s, 3H), 3.67 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 158.7,
134.4, 130.1, 126.0, 123.1, 113.9, 108.1, 107.6, 55.4, 35.0. LRMS calcd.
for M+ C12H13NO 187, found 187.
2-(3-Bromophenyl)-1-methylpyrrole (26):[25] 3-Bromobenzene-
sulfonyl chloride (0.255 g, 1 mmol) and 1-methylpyrrole (0.243 g,
3 mmol) affords 26 in 87 % (0.205 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 7.58 (s, 1H), 7.44 (d, J = 8.2 Hz, 1H), 7.35 (d, J = 7.8 Hz,
1H), 7.28 (t, J = 7.8 Hz, 1H), 6.75 (s, 1H), 6.30–6.20 (m, 2H), 3.69 (s,
3H). 13C NMR (100 MHz, CDCl3): δ = 135.5, 133.1, 131.4, 130.0, 129.7,
127.1, 124.5, 122.5, 109.5, 108.1, 35.2. LRMS calcd. for M+ C11H10BrN
235, found 235.
1-Benzyl-2-(4-nitrophenyl)pyrrole (27):[10a] 4-Nitrobenzenesulf-
onyl chloride (0.221 g, 1 mmol) and 1-benzylpyrrole (0.471 g,
3 mmol) affords 27 in 80 % (0.222 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 8.21 (d, J = 8.7 Hz, 2H), 7.48 (d, J = 8.7 Hz, 2H), 7.40–
7.26 (m, 3H), 7.04 (dd, J = 7.4, 1.6 Hz, 2H), 6.91 (dd, J = 2.7, 1.8 Hz,
1H), 6.49 (dd, J = 3.6, 1.7 Hz, 1H), 6.37 (dd, J = 3.7, 2.7 Hz, 1H), 5.25
(s, 2H). 13C NMR (100 MHz, CDCl3): δ = 145.1, 138.5, 137.0, 131.5,
127.9, 127.3, 126.7, 125.1, 124.8, 122.8, 110.6, 108.4, 50.1. LRMS
calcd. for M+ C17H14N2O2 278, found 278.
2-(4-Nitrophenyl)benzofuran (17):[22] 4-Nitrobenzenesulfonyl
chloride (0.221 g, 1 mmol) and benzofuran (0.177 g, 1.5 mmol) af-
fords 17 in 57 % (0.136 g) yield. 1H NMR (400 MHz, CDCl3): δ = 8.34
(d, J = 8.6 Hz, 2H), 8.03 (d, J = 8.6 Hz, 2H), 7.67 (d, J = 8.0 Hz, 1H),
7.58 (d, J = 8.0 Hz, 1H), 7.40 (t, J = 7.8 Hz, 1H), 7.29 (t, J = 7.8 Hz,
1H), 7.27 (s, 1H). 13C NMR (100 MHz, CDCl3): δ = 155.6, 153.4, 147.4,
136.4, 128.8, 126.0, 125.3, 124.5, 123.7, 121.8, 111.6, 105.2. LRMS
calcd. for M+ C14H9NO3 239, found 239.
2-[4-(Trifluoromethyl)phenyl]benzofuran (18):[22] 4-(Trifluoro-
methyl)benzenesulfonyl chloride (0.245 g, 1 mmol) and benzofuran
(0.177 g, 1.5 mmol) affords 18 in 63 % (0.165 g) yield. 1H NMR
(400 MHz, CDCl3): δ = 7.96 (d, J = 7.8 Hz, 2H), 7.70 (d, J = 7.8 Hz,
2H), 7.62 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.35 (t, J =
7.8 Hz, 1H), 7.29 (t, J = 7.8 Hz, 1H), 7.14 (s, 1H). 13C NMR (100 MHz,
CDCl3): δ = 155.3, 154.3, 133.8, 130.2 (q, J = 32.5 Hz), 129.0, 126.0
(q, J = 2.1 Hz), 125.2, 125.1, 124.1 (q, J = 271.8 Hz), 123.4, 111.5,
103.4. LRMS calcd. for M+ C15H9F3O 262, found 262.
2-(4-Chlorophenyl)benzofuran (19):[22] 4-Chlorobenzenesulfonyl
chloride (0.211 g, 1 mmol) and benzofuran (0.177 g, 1.5 mmol) af-
fords 19 in 60 % (0.137 g) yield. 1H NMR (400 MHz, CDCl3): δ = 7.79
(d, J = 7.8 Hz, 2H), 7.59 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H),
7.42 (d, J = 7.8 Hz, 2H), 7.31 (t, J = 7.8 Hz, 1H), 7.26 (t, J = 7.8 Hz,
1H), 7.01 (s, 1H). 13C NMR (100 MHz, CDCl3): δ = 155.0, 154.9, 134.4,
129.2 (2C), 129.1, 126.3, 124.7, 123.2, 121.1, 111.3, 101.9. LRMS calcd.
for M+ C14H9ClO 228, found 228.
2-(4-Fluorophenyl)benzofuran (20):[22] 4-Fluorobenzenesulfonyl
chloride (0.194 g, 1 mmol) and benzofuran (0.177 g, 1.5 mmol) af-
fords 20 in 73 % (0.155 g) yield. 1H NMR (400 MHz, CDCl3): δ = 7.87
(dd, J = 5.8, 5.5 Hz, 2H), 7.61 (d, J = 7.5 Hz, 1H), 7.55 (d, J = 8.0 Hz,
1H), 7.32 (t, J = 7.3 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H), 7.17 (t, J = 7.5 Hz,
2H), 6.98 (s, 1H). 13C NMR (100 MHz, CDCl3): δ = 163.0 (d, J =
248.7 Hz), 155.1, 155.0, 129.3, 126.9, 126.8 (d, J = 8.3 Hz), 124.4,
123.2, 121.0, 116.1 (d, J = 21.7 Hz), 111.3, 101.1 (d, J = 1.7 Hz). LRMS
calcd. for M+ C14H9FO 212, found 212.
1-(4-Fluorophenyl)-2-(4-nitrophenyl)pyrrole (28): 4-Nitro-
benzenesulfonyl chloride (0.221 g, 1 mmol) and 1-(4-fluorophenyl)-
pyrrole (0.483 g, 3 mmol) affords 28 in 74 % (0.209 g) yield. 1H NMR
(400 MHz, CDCl3): δ = 8.10 (d, J = 8.7 Hz, 2H), 7.25 (d, J = 8.7 Hz,
2H), 7.21–7.15 (m, 2H), 7.10 (t, J = 8.2 Hz, 2H), 7.00 (dd, J = 2.7,
1.7 Hz, 1H), 6.65 (dd, J = 3.6, 1.7 Hz, 1H), 6.43 (dd, J = 3.6, 2.9 Hz,
1H). 13C NMR (100 MHz, CDCl3): δ = 161.7 (d, J = 248.0 Hz), 145.6,
138.9, 136.0 (d, J = 3.2 Hz), 131.6, 127.7, 127.3 (d, J = 8.5 Hz), 126.9,
123.6, 116.3 (d, J = 22.8 Hz), 113.3, 110.2. Anal. Calcd for
C16H11FN2O2 (282.27): C, 68.08; H, 3.93; N, 9.92; found C, 68.25; H,
3.99; N, 10.08.
3-(4-Nitrophenyl)selenophene (29):[10c]. 4-Nitrobenzenesulfonyl
chloride (0.221 g, 1 mmol) and selenophene (0.196 g, 1.5 mmol)
affords 29 in 56 % (0.141 g) yield. 1H NMR (400 MHz, CDCl3): δ =
8.32 (dd, J = 2.5, 1.3 Hz, 1H), 8.25 (d, J = 8.6 Hz, 2H), 8.15 (dd, J =
5.5, 2.5 Hz, 1H), 7.71 (dd, J = 5.5, 1.3 Hz, 1H), 7.73 (d, J = 8.6 Hz,
2H). 13C NMR (100 MHz, CDCl3): δ = 146.7, 143.3, 142.4, 132.2, 129.1,
128.9, 127.1, 124.4. LRMS calcd. for M+ C10H7NO2Se 253, found 253.
3-(4-Bromophenyl)selenophene (30):[10c] 4-Bromobenzenesulf-
onyl chloride (0.255 g, 1 mmol) and selenophene (0.196 g,
1.5 mmol) affords 30 in 70 % (0.200 g) yield. 1H NMR (400 MHz,
CDCl3): δ = 8.11 (dd, J = 2.5, 1.3 Hz, 1H), 8.09 (dd, J = 5.5, 2.5 Hz,
1H), 7.63 (dd, J = 5.5, 1.3 Hz, 1H), 7.52 (d, J = 8.6 Hz, 2H), 7.45 (d,
J = 8.6 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ = 143.5, 136.2, 132.0,
131.4, 129.4, 128.3, 125.9, 121.1. LRMS calcd. for M+ C10H7BrSe 286,
found 286.
2-Phenylbenzofuran (21):[22] Benzenesulfonyl chloride (0.177 g,
1 mmol) and benzofuran (0.177 g, 1.5 mmol) affords 21 in 65 %
(0.126 g) yield. 1H NMR (400 MHz, CDCl3): δ = 7.89 (d, J = 7.8 Hz,
2H), 7.60 (d, J = 7.8 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 7.46 (t, J =
7.8 Hz, 2H), 7.35 (t, J = 7.8 Hz, 1H), 7.30 (t, J = 7.8 Hz, 1H), 7.25 (t,
J = 7.8 Hz, 1H), 7.04 (s, 1H). 13C NMR (100 MHz, CDCl3): δ = 156.0,
155.0, 130.6, 129.3, 128.9, 128.7, 125.1, 124.4, 123.1, 121.0, 111.3,
101.4. LRMS calcd. for M+ C14H10O 194, found 194.
2-(4-Methoxyphenyl)benzofuran (22):[22] 4-Methoxybenzenesulf-
onyl chloride (0.206 g, 1 mmol) and benzofuran (0.177 g, 1.5 mmol)
affords 22 in 57 % (0.128 g) yield. 1H NMR (400 MHz, CDCl3): δ =
7.80 (d, J = 7.8 Hz, 2H), 7.56 (d, J = 8.0 Hz, 1H), 7.50 (d, J = 8.0 Hz,
1H), 7.27 (t, J = 7.8 Hz, 1H), 7.24 (t, J = 7.8 Hz, 1H), 6.99 (d, J =
7.8 Hz, 2H), 6.89 (s, 1H), 3.87 (s, 3H). 13C NMR (100 MHz, CDCl3): δ =
160.1, 156.2, 154.8, 129.6, 126.6, 123.9, 123.5, 123.0, 120.7, 114.4,
111.1, 99.8, 55.5. LRMS calcd. for M+ C15H12O2 224, found 224.
2-(4-Bromophenyl)benzofuran (23):[22] 4-Bromobenzenesulfonyl
chloride (0.255 g, 1 mmol) and benzofuran (0.177 g, 1.5 mmol) af-
fords 23 in 81 % (0.221 g) yield. 1H NMR (400 MHz, CDCl3): δ = 7.73
(d, J = 7.8 Hz, 2H), 7.57 (d, J = 8.0 Hz, 1H), 7.56 (d, J = 7.8 Hz, 2H),
7.52 (d, J = 8.0 Hz, 1H), 7.31 (t, J = 7.8 Hz, 1H), 7.25 (t, J = 7.8 Hz,
1H), 7.02 (s, 1H). 13C NMR (100 MHz, CDCl3): δ = 155.0, 154.9, 132.1,
129.5, 129.2, 126.5, 124.7, 123.2, 122.6, 121.2, 111.3, 102.0. LRMS
calcd. for M+ C14H9BrO 272, found 272.
3-(4-Iodophenyl)selenophene (31):[10c] 4-Iodobenzenesulfonyl
chloride (0.302 g, 1 mmol) and selenophene (0.196 g, 1.5 mmol)
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affords 31 in 77 % (0.256 g) yield. 1H NMR (400 MHz, CDCl3): δ =
8.13–8.09 (m, 1H), 8.08 (dd, J = 5.5, 2.5 Hz, 1H), 7.72 (d, J = 8.6 Hz,
2H), 7.62 (dd, J = 5.5, 1.3 Hz, 1H), 7.33 (d, J = 8.6 Hz, 2H). 13C NMR
(100 MHz, CDCl3): δ = 143.6, 137.9, 136.8, 131.4, 129.3, 128.6, 126.0,
92.5. LRMS calcd. for M+ C10H7ISe 334, found 334.
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Keywords: Palladium · Heterogeneous catalysis · Direct
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Received: October 24, 2019
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Full Paper
Direct Arylation
S. Mao, X. Shi, J.-F. Soulé,*
H. Doucet* ............................................ 1–8
Direct Arylations of Heteroarenes
with Benzenesulfonyl Chlorides Us-
ing Pd/C Catalyst
The potential of 10 % Pd/C catalyst in chlorides were tolerated. Notably,
desulfitative direct arylation of hetero- C-halo bonds including C–I bonds on
arenes was investigated. Electron-with- the benzenesulfonyl chlorides re-
drawing as well as electron-donating mained untouched affording halo-sub-
substituents on the benzenesulfonyl stituted heteroaromatic derivatives.
DOI: 10.1002/ejoc.201901561
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim