Palladium-catalysed direct monoarylation of bithiophenyl derivatives or bis(thiophen-2-yl)methanone with aryl bromides

Article abstract of DOI:10.1002/ejic.201100294

Arylated bithiophenes, which are useful compounds due to their coordination and/or physical properties, can be easily prepared by palladium-catalysed C-H bond activation of heteroaromatics followed by arylation using electron-deficient aryl bromides. A va

Full text of DOI:10.1002/ejic.201100294

FULL PAPER
DOI: 10.1002/ejic.201100294
Palladium-Catalysed Direct Monoarylation of Bithiophenyl Derivatives or
Bis(thiophen-2-yl)methanone with Aryl Bromides
Karima Si Larbi,[a,b] Safia Djebbar,[a] and Henri Doucet*[b]
Keywords: Arylation / Heterocycles / Homogeneous catalysis / C-H activation / Palladium
Arylated bithiophenes, which are useful compounds due to
their coordination and/or physical properties, can be easily
prepared by palladium-catalysed C–H bond activation of
heteroaromatics followed by arylation using electron-de-
ficient aryl bromides. A variety of 5-arylated 2,2Ј-bithio-
phenyl derivatives have been prepared. Good yields were
generally obtained by using the air-stable [PdCl(dppb)-
(C3H5)] complex as catalyst. A range of functions on the aryl
bromide, such as acetyl, formyl, ester, nitrile, trifluoromethyl,
fluoro and hydroxyalkyl, are tolerated.
Introduction
The search for an easy access to a variety of arylated
bithiophene derivatives is an important field of research in
organometallic and materials chemistry due to the coordi-
nation and/or physical properties of some of these com-
pounds.[1,2] Palladium-catalysed Suzuki, Stille and Negishi
cross-coupling reactions between 5-halo-2,2Ј-bithiophenyl
derivatives and organometallic derivatives or between orga-
nometallic bithiophenyls and aryl halides are some of the
most important methods for the synthesis of such com-
pounds.[3–6] However, these reactions require the prepara-
tion of an organometallic derivative of the (hetero)aro-
matics and provide an organometallic salt (MX) as a by-
product (Scheme 1).
Ohta et al. reported in 1990 that the direct 2- or 5-aryl-
ation of several heteroaromatics, including thiophenes, with
aryl halides proceeds in moderate to good yields by using
[Pd(PPh3)4] as the catalyst.[7] Since then, the palladium-cat-
alysed direct arylation of heteroaryl derivatives with aryl
halides has proved to be a very powerful method for the
synthesis of a wide range of arylated heteroarenes.[8,9] The
direct arylation of quite simple thiophene derivatives has
been widely explored,[10] whereas the palladium-catalysed
direct arylation of polythiophenes has attracted less atten-
tion.[11] Some examples of the preparation of 5,5Ј-di-
arylated bithiophenyls have been described. For example,
Miura and co-workers reported the 5Ј-arylation of 5-aryl-
2,2Ј-bithiophenes in 51–91% yields using 10 mol-%
Pd(OAc)2 in combination with 20 mol-% P(biphenyl-2-
Scheme 1.
yl)(tBu)2 as the catalyst and Cs2CO3 as the base.[11a] Simi-
larly, the arylation of 5-(4-methoxyphenyl)-2,2Ј-bithi-
ophenyl with ethyl 4-iodobenzoate gave the 5Ј-arylated
product in 33% yield by using [PdCl2(PPh3)2], AgNO3/KF
and DMSO.[11c] An example of the diarylation of 2,2Ј-bithi-
ophenyl at C-5 and C-5Ј has also been reported by Fagnou
and co-workers.[11e] On the other hand, very few examples
of the preparation of monoarylated bithiophenyls by direct
arylation reactions have been reported. To prepare push–
pull systems, the reaction of 3,4-ethylenedioxythiophene
with 4-iodoanisole gave the monoarylated bithiophenyl in
30% yield.[11d]
We now report the conditions for the direct monoaryl-
ation at C-5 of 2,2Ј-bithiophenyl derivatives and Bis-
(thiophen-2-yl)methanone with para-, meta- and ortho-sub-
stituted aryl bromides as well as heteroaryl bromides using
a relatively low loading of an air-stable catalyst.
[a] Laboratoire d’hydrométallurgie et chimie inorganique
moléculaire, Faculté de Chimie, U.S.T.H.B.,
Bab-Ezzouar, Alger
[b] Institut Sciences Chimiques de Rennes, UMR 6226 CNRS –
Université de Rennes 1, “Catalyse et Organometalliques”,
Campus de Beaulieu, 35042 Rennes, France
Fax: +33-2-23236939
Results and Discussion
To determine the reactivity of 2,2Ј-bithiophenyl in palla-
dium-catalysed direct arylation reactions, a series of direct
E-mail: henri.doucet@univ-rennes1.fr
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arylations in the presence of 4-bromobenzonitrile as the Table 1. Palladium-catalysed coupling of 2,2Ј-bithiophenyl with
para-substituted aryl bromides (Scheme 2).[a]
coupling partner were carried out under several reaction
conditions. Our objective was to obtain the monoarylated
compound 1 (Scheme 2). We first explored the activity of
[PdCl(C3H5)(dppb)] as we have recently demonstrated that
it is one of the best catalysts for the direct arylation of some
furans, thiophenes and thiazoles.[9d,10i] However, the forma-
tion of 5,5Ј-diarylated 2,2Ј-bithiophenyl in this reaction is
possible. To minimize the formation of this side-product, we
employed an excess of 2,2Ј-bithiophenyl. Thus, the yields of
the reactions are based on the molar amount of the aryl
bromide used. As 2,2Ј-bithiophenyl is stable, the excess can
be recovered at the end of the reaction. We observed that
by using 3 equiv. of 2,2Ј-bithiophenyl in the presence of
only 1 mol-% of this catalyst with KOAc as the base and
DMAc as the solvent, compound 1 was obtained in 74%
yield. As expected, the use of a smaller excess of 2,2Ј-bi-
thiophenyl (1.5–2 equiv.) led to the formation of larger
amounts of the 5,5Ј-diarylated product.
Scheme 2. Coupling of 2,2Ј-bithiophenyls with aryl bromides.
Then the scope of the monoarylation of 2,2Ј-bithio-
phenyl was investigated by using 1 mol-% [PdCl(C3H5)-
(dppb)] as the catalyst and 3 equiv. of 2,2Ј-bithiophenyl
with other aryl bromides (Scheme 2, Tables 1, 2 and 3).
First, we studied the reactivities of para-substituted aryl
bromides (Table 1). In the presence of electron-deficient
aryl bromides such as 4-bromoacetophenone, methyl 4-bro-
mobenzoate, 4-bromobenzonitrile or 1-bromo-4-(trifluoro-
methyl)benzene and 1 mol-% of catalyst, the products 2–6
were obtained in 69–73% yields (Table 1, Entries 2–6).
Products 2 and 6 have previously been prepared in 65 and
69% yields by Stille or Suzuki coupling of (2,2Ј-bithio-
phenyl-5-yl)boronic acid or 2-(tributylstannyl)thiophene
with aryl bromides.[2d,4a]
Note that even 1-bromo-4-chlorobenzene could be em-
ployed to give 7 in 67% yield. In the course of this reaction,
no cleavage of the C–Cl bond was observed, allowing for
further transformations (Table 1, Entry 7). 1-Bromo-4-fluo-
robenzene was also successfully coupled with 2,2Ј-bi-
2,2Ј-bithiophenyl (3 equiv.), aryl bromide (1 equiv.), KOAc
[a] Reagents and conditions: [PdCl(C3H5)(dppb)] (0.01 equiv.),
thiophenyl to give 8 in a slightly lower yield of 64% due
to an incomplete conversion of this aryl bromide (Table 1,
Entry 8). A moderate yield of 52% of 9 was obtained in the
presence of the non-activated aryl bromide bromobenzene
(Table 1, Entry 9). On the other hand, with the electron-
(2 equiv.), DMAc, 150 °C, 16 h. [b] Isolated yields.
A similar reactivity was observed in the presence of meta-
rich 1-bromo-4-tert-butylbenzene as coupling partner, the substituted aryl bromides (Table 2). The coupling reactions
expected product 10 was not detected (Table 1, Entry 10). with 3-bromoacetophenone, 1-bromo-3-(trifluoromethyl)-
Therefore, this procedure is limited to the use of electron- benzene and 1-bromo-3,5-bis(trifluoromethyl)benzene gave
poor or neutral aryl bromides.
11–13 in 70–74% yields (Table 2, Entries 1–3). The reac-
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Palladium-Catalysed Monoarylation with Aryl Bromides
tions of 2,2Ј-bithiophenyl with ortho-substituted aryl bro-
Palladium chemistry involving heterocycles has its own
mides were also examined. Palladium-catalysed reactions unique characteristics stemming from the inherently dif-
with such aryl bromides are sometimes more difficult due ferent coordination and electronic properties of heterocy-
to the steric or coordination properties of the ortho substit- cles in comparison to the corresponding carbocyclic aryl
uent. Good yields were obtained in the presence of 2-bro- compounds. Pyridines and quinolines are both π-electron-
mobenzonitrile or 1-bromonaphthalene (Table 2, Entries 4 deficient, and the oxidative addition of bromopyridines
and 7). On the other hand, the coupling reactions with 2- and -quinolines to palladium complexes is generally not the
bromobenzaldehyde and (2-bromophenyl)methanol led to rate-limiting step for most palladium-catalysed reactions.
15 and 16, respectively, in lower yields due to the formation We observed that the reactions of 3- and 4-bromopyridines,
of unidentified side-products (Table 2, Entries 5 and 6). 3-bromoquinoline, 4-bromoisoquinoline and 5-bromopyr-
Note that even 9-bromoanthracene could be coupled suc- imidine in the presence of 1 mol-% [PdCl(C3H5)(dppb)]
cessfully to give 18 in good yield (Table 2, Entry 8). Such gave 19–23 in 70–75% yields without poisoning of the cata-
coupling reactions with anthracene derivatives should allow lyst by coordination of the nitrogen atom to the palladium
the preparation of very useful compounds for materials catalyst (Table 3). Note that the products 19 and 20 have
chemistry.[12]
previously been prepared by Kumada coupling by using
(2,2Ј-bithiophenyl-5-yl)magnesium bromide with 3- and 4-
bromopyridine, respectively, as the coupling partners.[6c]
However, low to moderate yields of 51 and 14%, respec-
tively, were obtained. Moreover, 22 was obtained in only
35% yield by Stille coupling of 4-bromisoquinoline with 2-
(tributylstannyl)thiophene.[5a]
Table 2. Palladium-catalysed coupling of 2,2Ј-bithiophenyl with
meta- or ortho-substituted aryl bromides (Scheme 2).[a]
Table 3. Palladium-catalysed coupling of 2,2Ј-bithiophenyl with
heteroaryl bromides (Scheme 2).[a]
[a] Reagents and conditions: [PdCl(C3H5)(dppb)] (0.01 equiv.),
2,2Ј-bithiophenyl (3 equiv.), heteroaryl bromide (1 equiv.), KOAc
(2 equiv.), DMAc, 150 °C, 16 h. [b] Isolated yields.
The presence of substituents at C-3 and C-3Ј of the bi-
thiophenyls is known to be useful for materials chemis-
try.[13] To the best of our knowledge the direct arylation
of 3,3Ј-dimethyl-2,2Ј-bithiophenyl has never been reported.
Therefore, we examined the reactivity of this substrate with
a series of aryl bromides. The presence of such methyl sub-
stituents on bithiophenyl has only a minor influence on the
reaction, and yields very similar to those obtained with
2,2Ј-bithiophenyl were obtained (Table 4). Again, we em-
[a] Reagents and conditions: [PdCl(C3H5)(dppb)] (0.01 equiv.),
2,2Ј-bithiophenyl (3 equiv.), aryl bromide (1 equiv.), KOAc
(2 equiv.), DMAc, 150 °C, 16 h. [b] Isolated yields.
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Table 4. Palladium-catalysed coupling of 3,3Ј-dimethyl-2,2Ј-bi- ployed a variety of para-, meta- and ortho-substituted aryl
thiophenyl with aryl bromides (Scheme 2).[a]
bromides and also heteroaryl bromides. In all cases the de-
sired coupling products were obtained in good yields. Even
the coupling of the sterically very congested aryl bromide
9-bromoanthracene proceeded smoothly to give 32 in 67%
yield (Table 4, Entry 9).
The reactivities of two 5-substituted 2,2Ј-bithiophenyls
were also examined. Miura and Mori and their co-workers
previously reported the 5Ј-arylation of 5-aryl-2,2Ј-bi-
thiophenyl by using either expensive bases or large amounts
of an air-sensitive and expensive catalyst.[11a,11c] To access
more functionalized compounds we decided to employ 2,2Ј-
bithiophenyls bearing either formyl or acetyl functions at
C-5. The reaction of 1.5 equiv. of 2,2Ј-bithiophenyl-5-
carbaldehyde with 1 equiv. of 4-bromobenzonitrile and
methyl 4-bromobenzoate by using only 1 mol-% of
[PdCl(C3H5)(dppb)] and KOAc as base gave the target 5Ј-
arylated products 35 and 36 in 66 and 60% yields, respec-
tively (Table 5, Entries 1 and 2). Even the congested sub-
strate 9-bromoanthracene could be coupled to 2,2Ј-bi-
thiophenyl-5-carbaldehyde with this catalytic system to give
37 in 62% yield (Table 5, Entry 3). The reactivity of 2,2Ј-
bithiophenyl substituted at C-5 by an acetyl group was
found to be similar. Its coupling with 4-bromobenzonitrile
produced 39 in 66% yield (Table 5, Entry 5).
Table 5. Palladium-catalysed coupling of 5-substituted 2,2Ј-bi-
thiophenyls with aryl bromides (Scheme 2).[a]
[a] Reagents and conditions: [PdCl(C3H5)(dppb)] (0.01 equiv.), 5-
substituted 2,2Ј-bithiophenyls (1.5 equiv.), aryl bromide (1 equiv.),
KOAc (2 equiv.), DMAc, 150 °C, 16 h. [b] Isolated yields.
Then the reactivity of bis(thiophen-2-yl)methanone was
examined (Scheme 3). Because the formation of diarylated
compounds was possible, we employed 3 equiv. of this thio-
phene derivative. In the presence of 4- or 2-bromobenzoni-
[a] Reagents and conditions: [PdCl(C3H5)(dppb)] (0.01 equiv.),
3,3Ј-dimethyl-2,2Ј-bithiophenyl (3 equiv.), aryl bromide (1 equiv.),
KOAc (2 equiv.), DMAc, 150 °C, 16 h. [b] Isolated yields.
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Palladium-Catalysed Monoarylation with Aryl Bromides
trile and 1 mol-% of [PdCl(C3H5)(dppb)], the 5-arylation
products 40 and 41 were obtained in 70 and 68% yields,
respectively.
Experimental Section
General: N,N-Dimethylacetamide (DMAc; 99%) was purchased
from Acros. KOAc (99%), [Pd(C3H5)Cl]2 (56.5%), and 1,4-bis(di-
phenylphosphanyl)butane (dppb; 98%) were purchased from Alfa
Aesar. These compounds were not purified before use. H and 13C
1
NMR spectra were recorded with a Bruker 300 MHz spectrometer.
Preparation of the [PdCl(C3H5)(dppb)] Catalyst: An oven-dried
40 mL Schlenk tube equipped with a magnetic stirring bar was
charged with [Pd(C3H5)Cl]2 (182 mg, 0.5 mmol) and dppb (426 mg,
1 mmol) under argon. Anhydrous dichloromethane (10 mL) was
added, and then the solution was stirred at room temperature for
20 min. The solvent was removed in vacuo. The yellow powder was
used without purification. 31P NMR (81 MHz, CDCl3): δ = 19.3
(s) ppm.
Scheme 3. Coupling of bis(thiophen-2-yl)methanone with aryl bro-
mides.
General Procedure for the Coupling Reactions: In a typical experi-
ment, the aryl bromide (1 mmol), heteroaryl derivative (1.5–
3 mmol; see Tables 1, 2, 3, 4, 5), base (2 mmol) and
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) were dissolved in DMAc
(5 mL) under argon. The reaction mixture was stirred at 150 °C for
16 h. Then the solvent was evaporated, and the product was puri-
fied by silica gel column chromatography.
Finally, the coupling of 3-bromopyridine with 1,2-bis-
(thiophen-2-yl)ethane-1,2-dione was studied (Scheme 4).
However, a low yield of 42 was obtained due to the forma-
tion of several unidentified products. This might be a result
of the moderate thermal stability of these dithiophenes.
4-(2,2Ј-Bithiophenyl-5-yl)benzonitrile (1):[11a] The reaction of 4-bro-
mobenzonitrile (0.182 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g,
3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
1 in 74%
1
(0.198 g) yield. H NMR (300 MHz, CDCl3): δ = 7.70–7.60 (m, 4
H), 7.36 (d, J = 3.8 Hz, 1 H), 7.30–7.22 (m, 2 H), 7.18 (d, J =
3.8 Hz, 1 H), 7.07 (dd, J = 4.8, 3.8 Hz, 1 H) ppm.
Methyl 4-(2,2Ј-Bithiophenyl-5-yl)benzoate (2): The reaction of
methyl 4-bromobenzoate (0.215 g, 1 mmol), 2,2Ј-bithiophenyl
(0.498 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
Scheme 4. Coupling of 1,2-bis(thiophen-2-yl)ethane-1,2-dione with
3-bromopyridine.
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
2 in 70%
(0.210 g) yield. 1H NMR (300 MHz, CDCl3): δ = 8.07 (d, J =
8.3 Hz, 2 H), 7.67 (d, J = 8.3 Hz, 2 H), 7.36 (d, J = 3.8 Hz, 1 H),
7.35–7.25 (m, 2 H), 7.20 (d, J = 3.8 Hz, 1 H), 7.07 (dd, J = 4.8,
Conclusion
These results demonstrate that a low loading (1 mol-%) 3.8 Hz, 1 H), 3.95 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
166.7, 141.6, 138.4, 138.3, 137.1, 130.3, 128.8, 127.9, 125.2, 125.1,
124.8, 124.7, 124.1, 52.1 ppm. C16H12O2S2 (300.40): calcd. C 63.97,
H 4.03; found C 64.11, H 3.89.
of an air-stable catalyst in combination with a cheap and
non-toxic base can be employed for the palladium-catalysed
direct arylation of 2,2Ј-bithiophenyl derivatives and bis-
(thiophen-2-yl)methanone. The use of an excess of these
thiophenes allows the formation of compounds monoaryl-
ated at C-5 in good yields. This procedure compares favour-
ably with previously reported procedures as similar or
higher yields were obtained and there was no need to pre-
pare boron, tin or magnesium derivatives of the bithiophen-
yls. The major drawback of this procedure is the use of an
excess of the bithiophenyl derivatives. However, in large-
scale reactions it is possible to recycle most of the excess of
the bithiophenyls. By our procedure, satisfactory results
were obtained in the presence of electron-deficient aryl bro-
mides and with congested aryl bromides. A wide range of
functions on the aryl bromide, such as acetyl, benzoyl, for-
myl, ester, nitro, nitrile, trifluoromethyl, chloro, fluoro and
hydroxyalkyl, are tolerated. The major by-products of these
coupling reactions are AcOH/KBr instead of the metallic
salts obtained by more classical coupling procedures. For
these reasons this reaction should give an economically via-
ble and environmentally attractive access to arylated bithio-
1-[4-(2,2Ј-Bithiophenyl-5-yl)phenyl]ethanone (3):[14] The reaction of
4-bromoacetophenone (0.199 g, 1 mmol), 2,2Ј-bithiophenyl
(0.498 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
3 in 72%
(0.205 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.99 (d, J =
8.3 Hz, 2 H), 7.70 (d, J = 8.3 Hz, 2 H), 7.37 (d, J = 3.8 Hz, 1 H),
7.35–7.25 (m, 2 H), 7.20 (d, J = 3.8 Hz, 1 H), 7.07 (dd, J = 4.8,
3.8 Hz, 1 H), 2.60 (s, 3 H) ppm.
[4-(2,2Ј-Bithiophenyl-5-yl)phenyl](phenyl)methanone (4): The reac-
tion of 4-bromobenzophenone (0.261 g, 1 mmol), 2,2Ј-bithiophenyl
(0.498 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
4 in 73%
1
(0.253 g) yield. H NMR (300 MHz, CDCl3): δ = 7.95–7.75 (m, 4
H), 7.75–7.45 (m, 5 H), 7.39 (d, J = 3.8 Hz, 1 H), 7.35–7.24 (m, 2
H), 7.21 (d, J = 3.8 Hz, 1 H), 7.07 (dd, J = 4.8, 3.8 Hz, 1 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 196.3, 142.4, 138.8, 138.3, 138.1,
137.4, 136.5, 132.8, 131.4, 130.4, 128.7, 128.4, 125.7, 125.4, 125.3,
125.2, 124.5 ppm. C21H14OS2 (346.47): calcd. C 72.80, H 4.07;
found C 73.04, H 4.18.
5-(4-Nitrophenyl)-2,2Ј-bithiophenyl (5):[2d] The reaction of 1-bromo-
phene derivatives useful as ligands or in materials chemistry. 4-nitrobenzene (0.202 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g,
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K. Si Larbi, S. Djebbar, H. Doucet
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3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
2,2Ј-bithiophenyl (0.498 g, 3 mmol) and KOAc (0.196 g, 2 mmol)
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
5
in 69%
in the presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) af-
forded 13 in 70% (0.265 g) yield. H NMR (300 MHz, CDCl3): δ
1
(0.198 g) yield. 1H NMR (300 MHz, CDCl3): δ = 8.26 (d, J =
8.7 Hz, 2 H), 7.74 (d, J = 8.7 Hz, 2 H), 7.42 (d, J = 3.8 Hz, 1 H), = 8.00 (s, 2 H), 7.78 (s, 1 H), 7.38 (d, J = 3.8 Hz, 1 H), 7.33–7.22
7.35–7.25 (m, 2 H), 7.22 (d, J = 3.8 Hz, 1 H), 7.09 (dd, J = 4.8,
3.8 Hz, 1 H) ppm.
(m, 2 H), 7.21 (d, J = 3.8 Hz, 1 H), 7.07 (dd, J = 4.8, 3.8 Hz, 1 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 139.2, 139.0, 136.5, 136.1,
132.4 (q, J = 33.2 Hz), 128.0, 125.9, 125.2, 125 (m), 124.8, 124.4,
123.4 (q, J = 272.9 Hz), 120.6 (sept, J = 3.2 Hz) ppm. C16H8F6S2
(378.36): calcd. C 50.79, H 2.13; found C 50.70, H 2.04.
5-[4-(Trifluoromethyl)phenyl]-2,2Ј-bithiophenyl (6):[4a] The reaction
of 1-bromo-4-(trifluoromethyl)benzene (0.225 g, 1 mmol), 2,2Ј-bi-
thiophenyl (0.498 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 6 in
70% (0.217 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.71 (d, J
= 8.7 Hz, 2 H), 7.65 (d, J = 8.7 Hz, 2 H), 7.40–7.20 (m, 4 H), 7.09
(dd, J = 4.8, 3.8 Hz, 1 H) ppm.
2-(2,2Ј-Bithiophenyl-5-yl)benzonitrile (14): The reaction of 2-bro-
mobenzonitrile (0.182 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g,
3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 14 in 71%
(0.190 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.75 (d, J =
8.6 Hz, 1 H), 7.70–7.55 (m, 3 H), 7.50–7.35 (m, 1 H), 7.30–7.15 (m,
3 H), 7.06 (dd, J = 4.8, 3.8 Hz, 1 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 139.3, 137.8, 137.0, 136.6, 134.4, 133.0, 129.2, 128.3,
127.9, 127.5, 125.1, 124.7, 124.3, 118.8, 109.5 ppm. C15H9NS2
(267.37): calcd. C 67.38, H 3.39; found C 67.31, H 3.32.
5-(4-Chlorophenyl)-2,2Ј-bithiophenyl (7): The reaction of 1-bromo-
4-chlorobenzene (0.191 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g,
3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
7 in 67%
(0.185 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.54 (d, J =
8.2 Hz, 2 H), 7.37 (d, J = 8.2 Hz, 2 H), 7.30–7.10 (m, 4 H), 7.05
(dd, J = 4.8, 3.8 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
141.6, 137.2, 133.3, 132.6, 129.1, 127.9, 126.7, 124.7, 124.6, 123.8,
123.3 ppm. C14H9ClS2 (276.81): calcd. C 60.75, H 3.28; found C
60.59, H 3.40.
2-(2,2Ј-Bithiophenyl-5-yl)benzaldehyde (15): The reaction of 2-bro-
mobenzaldehyde (0.185 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g,
3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 15 in 63%
(0.170 g) yield. 1H NMR (300 MHz, CDCl3): δ = 10.27 (s, 1 H),
8.02 (d, J = 8.6 Hz, 1 H), 7.70–7.00 (m, 6 H), 6.97 (dd, J = 4.8,
3.8 Hz, 1 H), 6.91 (d, J = 3.6 Hz, 1 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 192.3, 139.9, 138.0, 137.8, 137.0, 134.5, 134.1, 131.4,
130.8, 128.7, 128.5, 128.4, 125.5, 124.7, 124.6 ppm. C15H10OS2
(270.37): calcd. C 66.63, H 3.73; found C 66.70, H 3.79.
5-(4-Fluorophenyl)-2,2Ј-bithiophenyl (8): The reaction of 1-bromo-
4-fluorobenzene (0.175 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g,
3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
8 in 64%
(0.166 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.58 (dd, J = 8.8,
3.5 Hz, 2 H), 7.30–7.05 (m, 7 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 162.8 (d, J = 237.5 Hz), 142.4, 137.7, 137.1, 130.8,
128.3, 127.7 (d, J = 8.1 Hz), 125.0, 124.9, 124.1, 124.0, 116.3 (d, J
= 21.8 Hz) ppm. C14H9FS2 (260.35): calcd. C 64.59, H 3.48; found
C 64.70, H 3.61.
[2-(2,2Ј-Bithiophenyl-5-yl)phenyl]methanol (16): The reaction of (2-
bromophenyl)methanol (0.187 g, 1 mmol), 2,2Ј-bithiophenyl
(0.498 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 16 in 58%
(0.158 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.59 (d, J =
8.6 Hz, 1 H), 7.52 (d, J = 8.6 Hz, 1 H), 7.45–7.35 (m, 2 H), 7.30–
7.20 (m, 2 H), 7.19 (d, J = 3.8 Hz, 1 H), 7.13 (d, J = 3.8 Hz, 1 H),
7.06 (dd, J = 4.8, 3.8 Hz, 1 H), 4.83 (s, 2 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 140.5, 138.4, 137.8, 137.2, 133.3, 130.6,
129.1, 128.4, 128.0, 127.9, 127.7, 124.5, 124.1, 123.8, 63.5 ppm.
C15H12OS2 (272.39): calcd. C 66.14, H 4.44; found C 66.21, H 4.37.
5-Phenyl-2,2Ј-bithiophenyl (9):[11b] The reaction of bromobenzene
(0.157 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g, 3 mmol) and KOAc
(0.196 g, 2 mmol) in the presence of [PdCl(C3H5)(dppb)] (6.8 mg,
0.01 mmol) afforded 9 in 52% (0.126 g) yield. 1H NMR (300 MHz,
CDCl3): δ = 7.63–7.58 (m, 2 H), 7.43–7.36 (m, 2 H), 7.33–7.12 (m,
5 H), 7.04 (dd, J = 4.8, 3.8 Hz, 1 H) ppm.
5-(1-Naphthyl)-2,2Ј-bithiophenyl (17):[11a] The reaction of 1-bromo-
naphthalene (0.207 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g, 3 mmol)
and KOAc (0.196 g, 2 mmol) in the presence of [PdCl(C3H5)(dppb)]
1-[3-(2,2Ј-Bithiophenyl-5-yl)phenyl]ethanone (11): The reaction of 3-
bromoacetophenone (0.199 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g,
3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 11 in 74%
(0.210 g) yield. 1H NMR (300 MHz, CDCl3): δ = 8.19 (s, 1 H), 7.87
(d, J = 7.7 Hz, 1 H), 7.78 (d, J = 7.8 Hz, 1 H), 7.49 (t, J = 7.8 Hz,
1 H), 7.31 (d, J = 3.8 Hz, 1 H), 7.30–7.20 (m, 2 H), 7.18 (d, J =
3.8 Hz, 1 H), 7.06 (dd, J = 4.8, 3.8 Hz, 1 H), 2.62 (s, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 198.2, 142.1, 138.1, 137.9, 137.5,
135.0, 130.3, 129.6, 128.4, 127.7, 125.5, 125.1, 125.0, 124.9, 124.3,
27.2 ppm. C16H12OS2 (284.40): calcd. C 67.57, H 4.25; found C
67.41, H 4.14.
1
(6.8 mg, 0.01 mmol) afforded 17 in 73% (0.213 g) yield. H NMR
(300 MHz, CDCl3): δ = 8.50–8.40 (m, 1 H), 8.05–7.90 (m, 2 H),
7.80–7.50 (m, 4 H), 7.40–7.20 (m, 4 H), 7.12 (dd, J = 4.8, 3.8 Hz,
1 H) ppm.
5-(9-Anthryl)-2,2Ј-bithiophenyl (18):[12a] The reaction of 9-bromo-
anthracene (0.257 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g, 3 mmol)
and KOAc (0.196 g, 2 mmol) in the presence of [PdCl(C3H5)(dppb)]
1
(6.8 mg, 0.01 mmol) afforded 18 in 67% (0.229 g) yield. H NMR
(300 MHz, CDCl3): δ = 8.57 (s, 1 H), 8.20–8.10 (m, 4 H), 7.60–
7.45 (m, 4 H), 7.44 (d, J = 3.6 Hz, 1 H), 7.35–7.25 (m, 2 H), 7.15
(d, J = 3.6 Hz, 1 H), 7.12 (dd, J = 4.8, 3.8 Hz, 1 H) ppm.
5-[3-(Trifluoromethyl)phenyl]-2,2Ј-bithiophenyl (12):[11a] The reac-
tion of 1-bromo-3-(trifluoromethyl)benzene (0.225 g, 1 mmol),
2,2Ј-bithiophenyl (0.498 g, 3 mmol) and KOAc (0.196 g, 2 mmol)
in the presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) af-
3-(2,2Ј-Bithiophenyl-5-yl)pyridine (19):[6c] The reaction of 3-bromo-
pyridine (0.158 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g, 3 mmol) and
KOAc (0.196 g, 2 mmol) in the presence of [PdCl(C3H5)(dppb)]
1
forded 12 in 71% (0.220 g) yield. H NMR (300 MHz, CDCl3): δ
= 7.86 (s, 1 H), 7.77 (d, J = 7.0 Hz, 1 H), 7.60–7.10 (m, 6 H), 7.07
(dd, J = 4.8, 3.8 Hz, 1 H) ppm.
1
(6.8 mg, 0.01 mmol) afforded 19 in 73% (0.177 g) yield. H NMR
(300 MHz, CDCl3): δ = 8.90 (s, 1 H), 8.54 (d, J = 4.2 Hz, 1 H),
7.88 (d, J = 8.2 Hz, 1 H), 7.40–7.20 (m, 5 H), 7.07 (dd, J = 4.8,
3.8 Hz, 1 H) ppm.
5-[3,5-Bis(trifluoromethyl)phenyl]-2,2Ј-bithiophenyl (13): The reac-
tion of 1-bromo-3,5-bis(trifluoromethyl)benzene (0.293 g, 1 mmol),
3498
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 3493–3502

Palladium-Catalysed Monoarylation with Aryl Bromides
4-(2,2Ј-Bithiophenyl-5-yl)pyridine (20):[6c] The reaction of 4-bromo-
pyridine hydrochloride (0.194 g, 1 mmol), 2,2Ј-bithiophenyl
(0.498 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 20 in 75%
(0.182 g) yield. 1H NMR (300 MHz, CDCl3): δ = 8.60 (d, J =
2 mmol) in the presence of [PdCl(C3H5)(dppb)] (6.8 mg,
0.01 mmol) afforded 26 in 70% (0.230 g) yield. 1H NMR
(300 MHz, CDCl3): δ = 8.05 (d, J = 8.3 Hz, 2 H), 7.66 (d, J =
8.3 Hz, 2 H), 7.32 (d, J = 5.1 Hz, 1 H), 7.28 (s, 1 H), 6.96 (d, J =
5.1 Hz, 1 H), 3.95 (s, 3 H), 2.27 (s, 3 H), 2.24 (s, 3 H) ppm. 13C
6.0 Hz, 2 H), 7.44 (d, J = 6.0 Hz, 2 H), 7.41 (d, J = 3.8 Hz, 1 H), NMR (75 MHz, CDCl3): δ = 166.8, 141.8, 138.4, 137.8, 136.8,
7.30–7.22 (m, 2 H), 7.18 (d, J = 3.8 Hz, 1 H), 7.05 (dd, J = 4.8,
3.8 Hz, 1 H) ppm.
130.7, 130.3, 130.2, 129.0, 128.7, 127.5, 125.3, 125.1, 52.1, 15.0,
14.9 ppm. C18H16O2S2 (328.45): calcd. C 65.82, H 4.91; found C
65.98, H 4.97.
3-(2,2Ј-Bithiophenyl-5-yl)quinoline (21): The reaction of 3-bromo-
quinoline (0.208 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g, 3 mmol)
and KOAc (0.196 g, 2 mmol) in the presence of [PdCl(C3H5)(dppb)]
5-(4-Chlorophenyl)-3,3Ј-dimethyl-2,2Ј-bithiophenyl (27): The reac-
tion of 1-bromo-4-chlorobenzene (0.191 g, 1 mmol), 3,3Ј-dimethyl-
2,2Ј-bithiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol)
in the presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) af-
1
(6.8 mg, 0.01 mmol) afforded 21 in 73% (0.214 g) yield. H NMR
(300 MHz, CDCl3): δ = 9.18 (s, 1 H), 8.20 (s, 1 H), 8.10 (d, J =
8.2 Hz, 1 H), 7.80 (d, J = 7.8 Hz, 1 H), 7.69 (t, J = 8.0 Hz, 1 H),
7.55 (t, J = 8.0 Hz, 1 H), 7.40–7.10 (m, 4 H), 7.07 (dd, J = 4.8,
3.8 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 148.5, 147.6,
139.6, 138.5, 137.4, 131.2, 129.8, 129.7, 128.4, 128.3, 128.2, 127.7,
127.6, 125.4, 125.3, 125.2, 124.5 ppm. C17H11NS2 (293.41): calcd.
C 69.59, H 3.78; found C 69.51, H 3.64.
1
forded 27 in 62% (0.189 g) yield. H NMR (300 MHz, CDCl3): δ
= 7.53 (d, J = 8.2 Hz, 2 H), 7.36 (d, J = 8.2 Hz, 2 H), 7.31 (d, J =
5.1 Hz, 1 H), 7.16 (s, 1 H), 6.97 (d, J = 5.1 Hz, 1 H), 2.26 (s, 3 H),
2.22 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 141.9, 137.6,
136.7, 133.2, 132.7, 130.2, 129.5, 129.1, 129.0, 126.7, 126.5, 125.2,
15.0, 14.9 ppm. C16H13ClS2 (304.86): calcd. C 63.04, H 4.30; found
C 63.17, H 4.47.
4-(2,2Ј-Bithiophenyl-5-yl)isoquinoline (22):[5a] The reaction of 4-bro-
moisoquinoline (0.208 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g,
3 mmol) and KOAc (0.196 g, 2 mmol) in the presence of
[PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 22 in 74%
(0.217 g) yield. 1H NMR (300 MHz, CDCl3): δ = 9.25 (s, 1 H), 8.66
(s, 1 H), 8.32 (d, J = 8.2 Hz, 1 H), 8.05 (d, J = 7.7 Hz, 1 H), 7.76
(t, J = 8.0 Hz, 1 H), 7.70 (t, J = 8.0 Hz, 1 H), 7.35–7.20 (m, 4 H),
7.07 (dd, J = 4.8, 3.8 Hz, 1 H) ppm.
3,3Ј-Dimethyl-5-(3-nitrophenyl)-2,2Ј-bithiophenyl (28): The reaction
of 1-bromo-3-nitrobenzene (0.202 g, 1 mmol), 3,3Ј-dimethyl-2,2Ј-
bithiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 28 in
69% (0.217 g) yield. 1H NMR (300 MHz, CDCl3): δ = 8.45 (s, 1
H), 8.14 (d, J = 8.3 Hz, 1 H), 7.88 (d, J = 8.3 Hz, 1 H), 7.57 (t, J
= 7.8 Hz, 1 H), 7.28 (d, J = 5.1 Hz, 1 H), 7.27 (s, 1 H), 6.96 (d, J
= 5.1 Hz, 1 H), 2.27 (s, 3 H), 2.24 (s, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 147.7, 139.1, 136.8, 136.0, 134.8, 130.0,
129.2, 128.9, 128.8, 126.7, 124.4, 123.9, 120.7, 118.9 ppm.
C16H13NO2S2 (315.41): calcd. C 60.93, H 4.15; found C 60.98, H
4.04.
5-(2,2Ј-Bithiophenyl-5-yl)pyrimidine (23): The reaction of 5-bromo-
pyrimidine (0.159 g, 1 mmol), 2,2Ј-bithiophenyl (0.498 g, 3 mmol)
and KOAc (0.196 g, 2 mmol) in the presence of [PdCl(C3H5)(dppb)]
1
(6.8 mg, 0.01 mmol) afforded 23 in 70% (0.171 g) yield. H NMR
(300 MHz, CDCl3): δ = 9.12 (s, 1 H), 8.95 (s, 2 H), 7.40–7.20 (m,
4 H), 7.10–7.00 (m, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
156.1, 151.9, 138.4, 135.3, 133.4, 127.3, 127.0, 124.9, 124.3, 123.8,
123.5 ppm. C12H8N2S2 (244.34): calcd. C 58.99, H 3.30; found C
59.14, H 3.32.
3-(3,3Ј-Dimethyl-2,2Ј-bithiophenyl-5-yl)benzaldehyde (29): The reac-
tion of 3-bromobenzaldehyde (0.185 g, 1 mmol), 3,3Ј-dimethyl-2,2Ј-
bithiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 29 in
1
81% (0.241 g) yield. H NMR (300 MHz, CDCl3): δ = 10.07 (s, 1
4-(3,3Ј-Dimethyl-2,2Ј-bithiophenyl-5-yl)benzonitrile (24): The reac-
tion of 4-bromobenzonitrile (0.182 g, 1 mmol), 3,3Ј-dimethyl-2,2Ј-
bithiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 24 in
73% (0.215 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.70–7.60
(m, 4 H), 7.33 (d, J = 5.1 Hz, 1 H), 7.28 (s, 1 H), 6.97 (d, J =
5.1 Hz, 1 H), 2.27 (s, 3 H), 2.24 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 140.7, 138.4, 138.0, 136.9, 132.7, 131.7, 130.3, 128.7,
128.2, 125.6, 125.5, 118.9, 110.4, 15.0, 14.9 ppm. C17H13NS2
(295.42): calcd. C 69.11, H 4.44; found C 68.89, H 4.35.
H), 8.10 (s, 1 H), 7.85 (d, J = 8.2 Hz, 1 H), 7.80 (d, J = 8.2 Hz, 1
H), 7.56 (t, J = 8.0 Hz, 1 H), 7.31 (d, J = 5.1 Hz, 1 H), 7.27 (s, 1
H), 6.97 (d, J = 5.1 Hz, 1 H), 2.26 (s, 3 H), 2.24 (s, 3 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 192.5, 141.8, 138.1, 137.3, 137.2,
135.6, 131.6, 130.6, 130.0, 129.0, 127.5, 126.7, 125.7, 15.4,
15.3 ppm. C17H14OS2 (298.42): calcd. C 68.42, H 4.73; found C
68.57, H 4.60.
2-(3,3Ј-Dimethyl-2,2Ј-bithiophenyl-5-yl)benzonitrile (30): The reac-
tion of 2-bromobenzonitrile (0.182 g, 1 mmol), 3,3Ј-dimethyl-2,2Ј-
bithiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 30 in
71% (0.210 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.73 (d, J
= 8.2 Hz, 1 H), 7.60–7.20 (m, 5 H), 6.98 (d, J = 5.1 Hz, 1 H), 2.27
(s, 3 H), 2.24 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 138.4,
137.7, 137.3, 136.9, 134.5, 133.0, 131.9, 130.4, 130.2, 129.3, 128.6,
127.4, 125.5, 118.9, 109.5, 15.0, 14.9 ppm. C17H13NS2 (295.42):
calcd. C 69.11, H 4.44; found C 68.97, H 4.57.
1-[4-(3,3Ј-Dimethyl-2,2Ј-bithiophenyl-5-yl)phenyl]ethanone (25): The
reaction of 4-bromoacetophenone (0.199 g, 1 mmol), 3,3Ј-dimethyl-
2,2Ј-bithiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol)
in the presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) af-
1
forded 25 in 74% (0.231 g) yield. H NMR (300 MHz, CDCl3): δ
= 7.94 (d, J = 8.3 Hz, 2 H), 7.57 (d, J = 8.3 Hz, 2 H), 7.28 (d, J =
5.1 Hz, 1 H), 7.27 (s, 1 H), 6.96 (d, J = 5.1 Hz, 1 H), 2.63 (s, 3 H),
2.27 (s, 3 H), 2.24 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
192.2, 140.6, 137.5, 136.7, 135.7, 134.6, 129.9, 129.2, 128.1, 127.9,
126.6, 124.3, 124.2, 25.5, 13.9, 13.8 ppm. C18H16OS2 (312.45):
calcd. C 69.19, H 5.16; found C 69.17, H 5.34.
3,3Ј-Dimethyl-5-(1-naphthyl)-2,2Ј-bithiophenyl (31): The reaction of
1-bromonaphthalene (0.207 g, 1 mmol), 3,3Ј-dimethyl-2,2Ј-bi-
thiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 31 in
Methyl 4-(3,3Ј-Dimethyl-2,2Ј-bithiophenyl-5-yl)benzoate (26): The 62% (0.198 g) yield. 1H NMR (300 MHz, CDCl3): δ = 8.45–8.35
reaction of methyl 4-bromobenzoate (0.215 g, 1 mmol), 3,3Ј-di-
methyl-2,2Ј-bithiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g,
(m, 1 H), 8.00–7.75 (m, 2 H), 7.65–7.45 (m, 4 H), 7.32 (d, J =
5.1 Hz, 1 H), 7.15 (s, 1 H), 6.99 (d, J = 5.1 Hz, 1 H), 2.31 (s, 3 H),
Eur. J. Inorg. Chem. 2011, 3493–3502
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3499

K. Si Larbi, S. Djebbar, H. Doucet
2.29 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 137.0, 136.9, 5Ј-(9-Anthryl)-2,2Ј-bithiophenyl-5-carbaldehyde (37): The reaction
FULL PAPER
134.3, 132.7, 132.0, 130.8, 130.6, 130.2, 128.8, 128.7, 128.3, 126.8,
126.4, 126.2, 125.7, 125.5, 125.4, 15.4, 15.3 ppm. C20H16S2
(320.47): calcd. C 74.96, H 5.03; found C 75.08, H 5.12.
of 9-bromoanthracene (0.257 g, 1 mmol), 2,2Ј-bithiophenyl-5-carb-
aldehyde (0.291 g, 1.5 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 37 in
62% (0.230 g) yield. 1H NMR (300 MHz, CDCl3): δ = 9.91 (s, 1
H), 8.58 (s, 1 H), 8.09 (d, J = 8.0 Hz, 2 H), 7.96 (d, J = 8.0 Hz, 2
H), 7.71 (d, J = 3.5 Hz, 1 H), 7.58 (d, J = 3.6 Hz, 1 H), 7.57–7.40
(m, 4 H), 7.32 (d, J = 3.6 Hz, 1 H), 7.17 (d, J = 3.5 Hz, 1 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 182.6, 147.0, 141.7, 141.2, 137.4,
137.3, 131.6, 131.2, 130.8, 128.6, 128.5, 127.2, 126.4, 126.3, 126.2,
125.4, 124.3 ppm. C23H14OS2 (370.49): calcd. C 74.56, H 3.81;
found C 74.67, H 3.87.
5-(9-Anthryl)-3,3Ј-dimethyl-2,2Ј-bithiophenyl (32): The reaction of
9-bromoanthracene (0.257 g, 1 mmol), 3,3Ј-dimethyl-2,2Ј-bi-
thiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 32 in
67% (0.248 g) yield. 1H NMR (300 MHz, CDCl3): δ = 8.54 (s, 1
H), 8.06 (d, J = 7.5 Hz, 4 H), 7.55–7.45 (m, 4 H), 7.34 (d, J =
5.1 Hz, 1 H), 7.02 (s, 1 H), 7.00 (d, J = 5.1 Hz, 1 H), 2.36 (s, 3 H),
2.35 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 136.8, 135.0,
134.9, 131.0, 130.3, 129.9, 129.4, 128.8, 128.1, 127.4, 127.0, 126.6,
125.5, 124.7, 124.1, 123.8, 17.0, 16.9 ppm. C24H18S2 (370.53): calcd.
C 77.80, H 4.90; found C 77.97, H 5.01.
5Ј-Pyridin-3-yl-2,2Ј-bithiophenyl-5-carbaldehyde (38): The reaction
of 3-bromopyridine (0.158 g, 1 mmol), 2,2Ј-bithiophenyl-5-carbal-
dehyde (0.291 g, 1.5 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 38 in
65% (0.176 g) yield. 1H NMR (300 MHz, CDCl3): δ = 9.86 (s, 1
H), 8.87 (s, 1 H), 8.55 (d, J = 4.7 Hz, 1 H), 7.85 (d, J = 8.0 Hz, 1
H), 7.68 (d, J = 4.0 Hz, 1 H), 7.45–7.30 (m, 4 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 182.4, 149.1, 146.8, 146.4, 142.0, 141.8,
137.2, 136.4, 132.8, 129.5, 127.1, 125.3, 124.4, 123.7 ppm.
C14H9NOS2 (271.36): calcd. C 61.97, H 3.34; found C 62.10, H
3.41.
3-(3,3Ј-Dimethyl-2,2Ј-bithiophenyl-5-yl)pyridine (33): The reaction
of 3-bromopyridine (0.158 g, 1 mmol), 3,3Ј-dimethyl-2,2Ј-bi-
thiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 33 in
74% (0.201 g) yield. 1H NMR (300 MHz, CDCl3): δ = 8.86 (s, 1
H), 8.48 (d, J = 4.7 Hz, 1 H), 7.80 (d, J = 8.0 Hz, 1 H), 7.40–7.10
(m, 3 H), 6.93 (d, J = 5.1 Hz, 1 H), 2.27 (s, 3 H), 2.24 (s, 3 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 147.4, 145.6, 138.2, 136.7,
135.7, 131.5, 129.3, 129.1, 127.8, 126.1, 124.3, 122.6, 13.9,
13.8 ppm. C15H13NS2 (271.40): calcd. C 66.38, H 4.83; found C
66.27, H 4.94.
4-(5Ј-Acetyl-2,2Ј-bithiophenyl-5-yl)benzonitrile (39): The reaction of
4-bromobenzonitrile (0.182 g, 1 mmol), 1-(2,2Ј-bithiophenyl-5-yl)-
ethanone (0.312 g, 1.5 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 39 in
66% (0.204 g) yield. 1H NMR (300 MHz, CDCl3): δ = 7.73–7.66
(m, 4 H), 7.62 (d, J = 4.0 Hz, 1 H), 7.38 (d, J = 4.0 Hz, 1 H), 7.33
(d, J = 4.0 Hz, 1 H), 7.24 (d, J = 4.0 Hz, 1 H), 2.58 (s, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 189.7, 144.1, 142.4, 141.9, 137.1,
137.0, 132.7, 132.2, 126.1, 125.5, 125.2, 124.0, 118.0, 110.4,
25.9 ppm. C17H11NOS2 (309.41): calcd. C 65.99, H 3.58; found C
65.87, H 3.41.
4-(3,3Ј-Dimethyl-2,2Ј-bithiophenyl-5-yl)isoquinoline (34): The reac-
tion of 4-bromoisoquinoline (0.208 g, 1 mmol), 3,3Ј-dimethyl-2,2Ј-
bithiophenyl (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 34 in
75% (0.241 g) yield. 1H NMR (300 MHz, CDCl3): δ = 9.25 (s, 1
H), 8.67 (s, 1 H), 8.35 (d, J = 8.2 Hz, 1 H), 8.03 (d, J = 7.7 Hz, 1
H), 7.73 (t, J = 8.0 Hz, 1 H), 7.71 (t, J = 8.0 Hz, 1 H), 7.30 (d, J
= 5.1 Hz, 1 H), 7.19 (s, 1 H), 6.96 (d, J = 5.1 Hz, 1 H), 2.27 (s, 3
H), 2.24 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 152.8,
143.7, 137.5, 137.4, 137.1, 134.4, 131.4, 131.3, 130.7, 129.3, 128.8,
128.4, 127.8, 126.6, 125.7, 125.1, 15.4, 15.3 ppm. C19H15NS2
(321.46): calcd. C 70.99, H 4.70; found C 71.12, H 4.85.
4-[5-(Thiophen-2-ylcarbonyl)thiophen-2-yl]benzonitrile (40): The re-
action of 4-bromobenzonitrile (0.182 g, 1 mmol), bis(thiophen-2-
yl)methanone (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in
the presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
1
40 in 70% (0.207 g) yield. H NMR (300 MHz, CDCl3): δ = 7.93
(d, J = 3.8 Hz, 1 H), 7.90 (d, J = 4.0 Hz, 1 H), 7.79 (d, J = 8.0 Hz,
2 H), 7.71 (d, J = 8.0 Hz, 2 H), 7.80–7.70 (m, 1 H), 7.48 (d, J =
4.0 Hz, 1 H), 7.22 (dd, J = 4.8, 4.0 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 178.3, 149.3, 143.5, 142.4, 137.4, 134.0,
133.9, 133.2, 132.9, 128.1, 126.7, 125.6, 118.4, 112.2 ppm.
C16H9NOS2 (295.38): calcd. C 65.06, H 3.07; found C 65.14, H
3.20.
4-(5Ј-Formyl-2,2Ј-bithiophenyl-5-yl)benzonitrile (35): The reaction
of 4-bromobenzonitrile (0.182 g, 1 mmol), 2,2Ј-bithiophenyl-5-car-
baldehyde (0.291 g, 1.5 mmol) and KOAc (0.196 g, 2 mmol) in the
presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded 35 in
66% (0.195 g) yield. 1H NMR (300 MHz, CDCl3): δ = 9.91 (s, 1
H), 7.75–7.70 (m, 5 H), 7.45–7.20 (m, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 181.5, 145.1, 142.2, 141.2, 136.6, 136.3,
131.9, 131.6, 126.2, 125.2, 125.0, 123.7, 117.6, 110.2 ppm.
C16H9NOS2 (295.38): calcd. C 65.06, H 3.07; found C 65.24, H
3.14.
2-[5-(Thiophen-2-ylcarbonyl)thiophen-2-yl]benzonitrile (41): The re-
action of 2-bromobenzonitrile (0.182 g, 1 mmol), bis(thiophen-2-
yl)methanone (0.582 g, 3 mmol) and KOAc (0.196 g, 2 mmol) in
the presence of [PdCl(C3H5)(dppb)] (6.8 mg, 0.01 mmol) afforded
Methyl 4-(5Ј-Formyl-2,2Ј-bithiophenyl-5-yl)benzoate (36): The reac-
tion of methyl 4-bromobenzoate (0.215 g, 1 mmol), 2,2Ј-bi-
thiophenyl-5-carbaldehyde (0.291 g, 1.5 mmol) and KOAc (0.196 g,
2 mmol) in the presence of [PdCl(C3H5)(dppb)] (6.8 mg,
0.01 mmol) afforded 36 in 60% (0.197 g) yield. 1H NMR
(300 MHz, CDCl3): δ = 9.90 (s, 1 H), 8.09 (d, J = 8.3 Hz, 2 H),
7.75–7.68 (m, 3 H), 7.41 (d, J = 4.0 Hz, 1 H), 7.38 (d, J = 4.0 Hz,
1
41 in 68% (0.201 g) yield. H NMR (300 MHz, CDCl3): δ = 7.95
(d, J = 3.8 Hz, 1 H), 7.91 (d, J = 4.0 Hz, 1 H), 7.80–7.45 (m, 6 H),
7.22 (dd, J = 4.8, 4.0 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 178.6, 147.0, 144.2, 142.6, 136.5, 134.7, 134.1, 133.8, 133.6,
133.5, 130.1, 129.1, 128.4, 128.3, 118.5, 110.5 ppm. C16H9NOS2
(295.38): calcd. C 65.06, H 3.07; found C 65.01, H 3.22.
1 H), 7.32 (d, J = 4.0 Hz, 1 H), 3.96 (s, 3 H) ppm. 13C NMR 1-(5-Pyridin-3-ylthiophen-2-yl)-2-(thiophen-2-yl)ethane-1,2-dione
(75 MHz, CDCl3): δ = 182.5, 166.6, 146.6, 144.5, 142.0, 137.6, (42): The reaction of 3-bromopyridine (0.158 g, 1 mmol), 1,2-bis-
137.3, 136.5, 130.4, 129.5, 127.2, 125.6, 125.5, 124.4, 52.3 ppm.
C17H12O3S2 (328.41): calcd. C 62.17, H 3.68; found C 62.27, H
3.60.
(thiophen-2-yl)ethane-1,2-dione (0.666 g, 3 mmol) and KOAc
(0.196 g, 2 mmol) in the presence of [PdCl(C3H5)(dppb)] (6.8 mg,
0.01 mmol) afforded 42 in 21% (0.063 g) yield. 1H NMR
3500
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 3493–3502

Palladium-Catalysed Monoarylation with Aryl Bromides
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(300 MHz, CDCl3): δ = 9.00 (s, 1 H), 8.65 (d, J = 4.7 Hz, 1 H),
8.14 (d, J = 4.0 Hz, 1 H), 8.11 (d, J = 4.0 Hz, 1 H), 7.99 (d, J =
8.2 Hz, 1 H), 7.89 (d, J = 4.9 Hz, 1 H), 7.47 (d, J = 4.0 Hz, 1 H),
7.41 (dd, J = 8.2, 4.7 Hz, 1 H), 7.26 (t, J = 4.0 Hz, 1 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 181.9, 181.7, 152.2, 150.3, 147.4,
138.4, 138.2, 138.1, 137.8, 137.5, 133.6, 129.1, 128.7, 125.5,
123.9 ppm. C15H9NO2S2 (299.37): calcd. C 60.18, H 3.03; found C
60.31, H 3.10.
Acknowledgments
We thank the Centre National de la Recherche Scientifique
(CNRS) and “Rennes Metropole” for providing financial support.
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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3501

K. Si Larbi, S. Djebbar, H. Doucet
FULL PAPER
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Received: March 24, 2011
Published Online: July 13, 2011
3502
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Eur. J. Inorg. Chem. 2011, 3493–3502