Microwave-assisted synthesis of novel perimidinium salts as N-heterocyclic carbene precursors: Involvement in palladium-catalyzed cross-coupling reactions

Article abstract of DOI:10.1007/s10593-015-1732-3

[Figure not available: see fulltext.] In the current study, five novel perimidinium chlorides were synthesized in good yields by reaction of 1-(3-methylbenzyl)perimidine with five different alkyl chlorides under microwave irradiation in 30 minutes. Synthe

Full text of DOI:10.1007/s10593-015-1732-3

DOI 10.1007/s10593-015-1732-3
Chemistry of Heterocyclic Compounds 2015, 51(6), 563–567
Microwave-assisted synthesis of novel perimidinium salts
as N-heterocyclic carbene precursors:
involvement in palladium-catalyzed cross-coupling reactions
Gulnihan Onar1, Mert Olgun Karatas1*, Bülent Alici1, Engin Cetinkaya2
1 Department of Chemistry, Faculty of Arts and Sciences, Inonu University,
Road of Elazig, 15th km., Post Office Box No: 44280, Malatya, Turkey
e-mail: mert.karatas@inonu.edu.tr
2 Department of Chemistry, Faculty of Sciences, Ege University,
Neighborhood of Erzene, Bornova Post Office Box No: 35040, Izmir, Turkey
e-mail: engin.cetinkaya@ege.edu.tr
Published in Khimiya Geterotsiklicheskikh Soedinenii,
2015, 51(6), 563–567
Submitted February 2, 2015
Accepted after revision May 20, 2015
H
N
N
+
MW, 1 h
Cl–
Me
R
N
N
5 novel perimidinium salts
as N-heterocyclic carbene precursors
In the current study, five novel perimidinium chlorides were synthesized in good yields by reaction of 1-(3-methylbenzyl)perimidine
with five different alkyl chlorides under microwave irradiation in 30 minutes. Synthesized compounds were characterized by IR, 1H, 13
C
NMR spectroscopic methods and elemental analyses. Performance of in situ formed catalytic system which consist of the perimidinium
salts and Pd(OAc)2 was investigated for Heck and Suzuki reactions in aqueous media, and desired products were obtained in good yields.
Keyword: carbenes, palladium, perimidine, catalysis, Heck reaction, microwave irradiation, Suzuki reaction.
The formation of C–C bond is one of the most important
reaction in organic synthesis due to its wide application in
synthesis of natural and bioactive compounds. Palladium-
catalyzed cross-coupling reactions are especially attractive
because of their usefulness for forming of C–C bonds. The
palladium-catalyzed cross coupling of aryl halides with
olefines, one of the most known and most utilized cross-
coupling reaction has been known as Mizoroki–Heck
reaction.1,2 The palladium-catalyzed cross-coupling reaction of
aryl halides or aryl triflates with arylboronic acid is known
as Suzuki reaction and applied to numerous C–C bond
formation.3 Many articles with different Pd complexes and
conditions were published as application of these
reactions.4–9 For both reactions, choosing of ligand plays an
important role for efficacy of catalyst. Various type of
ligands were used in the palladium-catalyzed Heck and
Suzuki reactions10–12 and one of the most important ligand
type is N-heterocyclic carbene (NHC) and the first
application of the Pd–NHC-catalyzed Heck reaction was
reported by Herrmann.13 Strong electron-donating ability of
NHC ligands give their metal complexes stability to heat,
air, and moisture.14–19
Since the early 90s, various NHC ligands have been
reported. As NHC precursor,
imidazolium,14,15
imidazolinium,16,17 and benzimidazolium18,19 scaffolds were
used intensively, and very active catalytic systems were
prepared with not only palladium but also with various
transition metals. In spite of the rapid development of the
synthesis of NHC complexes and their application in
catalytic reactions, perimidine-based NHC's were not
studied sufficiently due to difficulties of producing of
perimidine derivatives compared with five-membered
analogs. Perimidine-based NHCs and its Rh complexes
were investigated first time in 2003 by Richeson and co-
workers20 but only a few perimidine-based catalysts have
been reported in literature so far by the other research groups.21–26
In addition to catalytic applications of perimidine
derivatives, their anti-inflammatory,27 antioxidant,28
antimicrobial,29 antibacterial,30 antitumor,31 and dyestuff32
properties were reported.
In the present study, we aimed to facile synthesis and
characterization of different perimidinium chlorides
bearing alkylated benzyl substituents on nitrogen atom and
also evaluation of catalytic activities of these salts in the
0009-3122/15/5106-0563©2015 Springer Science+Business Media New York
563

Chemistry of Heterocyclic Compounds 2015, 51(6), 563–567
Scheme 1
R
1) t-BuOK, DMSO
H
N
Cl
N
N
N
rt, 30 min
Cl–
+
Me
R
Me
DMF, MW
110°C, 30 min
2) 3-MeC6H4CH2Cl
MW, 110°C, 30 min
N
N
1
2a–e
a R = 2-Me, b R = 4-Me, c R = 2,4,6-Me3, d R = 2,3,4,5,6-Me5, e R = 3,4,5-(OMe)3
Pd-catalyzed Heck and Suzuki reactions. For this purpose,
firstly, 1-(3-methylbenzyl)perimidine (1) was synthesized
in 95% yield by reacting perimidine and 3-methylbenzyl
chloride in the presence of t-BuOK as a base in DMSO
solution at 110°C under microwave irradiation (Scheme 1).
IR spectra of compound 1 supports the structure of the
The Heck reaction is a very useful synthetic method for
particularly preparation of disubstituted olefins. For the
Heck reaction, very active catalytic systems containing
NHC ligand precursors have been reported in the
literature,16–19 including imidazolium, imidazolinium or
benzimidazolium salts. The use of Pd(OAc)2–perimidinium
salt catalytic system in this reaction is reported only by Tu
and co-workers, and this study is an isolated instance in
literature.23 They carried out the Heck reaction with n-butyl
acrylate and aryl halides and obtained the products in good
1
compound, as well as the data of H, 13C NMR and
elemental analysis. In the literature the synthesis of
1-alkylperimidines is reported in ethanol or methanol under
reflux conditions at longer reaction times.24,26
After the synthesis of compound 1, five perimidinium
salts 2a–e were synthesized by reaction of compound 1 and
five different alkyl chlorides in good yields (82–96%) at
110°C under microwave irradiation (Scheme 1). Thus, the
use of microwave irradiation shortens the reaction time
significantly at nearly the same temperature as compared
with literature data.23,24,26 If we consider the difficulties in
producing perimidine derivatives and the short reaction
time, the achieved yields are quite satisfactory. Elemental
analysis data are in unison with the structures of
compounds 2a–e. In 1H NMR spectra of compounds 2a–c,e,
NCHN proton signals are located at 10.30–11.65 ppm,
while in spectrum of compound 2d the signal of this proton
appears at 8.47 ppm. The reason for such a difference in
chemical shift probably is due to the magnetic anisotropy
shielding effect. These signals are consistent with general
acidic proton shift of the related imidazolium and benz-
imidazolium salts.17,18 IR spectra of compounds 2a–e
support the proposed structure, signals at 1656–1667 cm–1
indicate the presence of –N=C–N– group in the structure.
It is known that the mixtures of azolium and palladium
salts were used as precatalysts for Heck and Suzuki reac-
tions.16–18 In the Heck and Suzuki reactions, five perimidi-
nium salts 2 were used as NHC precursors. The azinium
salts 2 that we used as carbene precursors were stable
against air and moisture. We investigated the performance
of a catalytic system formed in situ from perimidinium
salts 2 and Pd(OAc)2 for Heck and Suzuki reactions in
aqueous media. The rate of coupling for both reactions is
dependent on temperature, solvent, base, and catalyst
loading. We have preferred to use DMF–H2O solvent
system because of cheapness, nontoxic, nonflammable, and
inexpensive properties of water. Besides, it benefits us
readily separation from organic phase. Various bases may
be used in Heck and Suzuki reactions such as t-BuOK,
K2CO3, KOH, NaOH, Cs2CO3.17 To chose the appropriate
base we have tested Cs2CO3 and t-BuOK, however,
noteworthy yields for the desired products were not
obtained using t-BuOK (Tables 1, entry 20, Tables 2, entry 13).
Table 1. Heck reaction between styrene
and 4-substituted bromobenzene derivatives in the presence
of Pd(OAc)2–perimidinium salt 2 system*
4-R1C6H4Br
Pd(OAc)2, 2a–e
R1
Cs2CO3
CH2
DMF, H2O
90°C, 4 h
Entry
R1
Perimidinium salt
Yield**, %
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
OMe
OMe
OMe
OMe
COMe
COMe
COMe
COMe
COMe
H
H
H
H
Me
Me
Me
Me
84
94
86
96
91
90
89
94
96
97
83
85
95
78
70
74
96
2a
2b
2c
2e
2a
2b
2c
2d
2e
2a
2b
2c
2e
2a
2b
2c
2e
2d
2e
2d
2d
–
CHO
CHO
CHO
CHO
CHO
97
90
<10***
<10*4
<10
* Load of the reagents: styrene (1.5 mmol), 4-R1C6H4Br (1 mmol),
Cs2CO3 (2 mmol), salt 2a–e (2 mol %), Pd(OAc)2 (1 mol %), DMF (2 ml),
H2O (2 ml).
** Yields are determined by GC and calculated based on the amount of
aryl bromide.
*** t-BuOK is used as a base.
*4 Reaction time 30 min.
564

Chemistry of Heterocyclic Compounds 2015, 51(6), 563–567
Table 2. Suzuki reaction between phenylboronic acid
yields (46–92%) at low catalyst loading. We used styrene and
substituted bromobenzene derivatives as reactants for the
model reaction. Good yields (70–97%) were obtained at 1 mol
% catalyst loading (Table 1, entries 1–19). Five different aryl
bromides were used. Both electron-rich and electron-poor aryl
bromides (4-bromoacetophenone, 4-bromotoluene, 4-bromo-
benzaldehyde, 4-bromoanisole, and bromobenzene) were
coupled successfully with styrene in the presence of Pd(OAc)
2/2a–e system, giving good yields of the desirable stilbenes in
mild reaction conditions. Catalytic effects of perimidinium
salts 2a–e are comparable for five ligand precursors.
The effect of the reaction time was tested in the reaction
of 4-bromobenzaldehyde and styrene using Pd(OAc)2/2d
catalytic system and Cs2CO3 as a base (Table 1, entries 18, 21).
As seen from Table 1, we did not obtain noteworthy yield
of the desired product in 30 min (entry 21). We also tested
Heck reaction in the absence of NHC precursor (entry 22);
in this case catalytic effect was not observed even in 4 h. It
corresponds to the literature data: thus, Demir and co-
workers showed that coupling reaction did not occur in the
absence of ligand precursors (reaction conditions: DMF–
H2O solvent system, Cs2CO3 as a base).18
Over the last 15 years the Pd-catalyzed Suzuki reaction
has become the method of choice for the synthesis of biaryl
and heterobiaryl compounds. For the Suzuki reaction, just
like for the Heck reaction, very active catalytic systems
containing NHC ligand precursors were reported in the litera-
ture,16–19 including imidazolium, imidazolinium or benzimi-
dazolium salts. Also in the case of the Suzuki reaction only
Tu and co-workers have reported the use of perimidinium/Pd
(OAc)2 catalytic system.23 They carried out the reaction of
phenylboronic acid with iodobenzene or bromobenzene and
obtained good yields (49–95%) at low catalyst loading.
In this study, we used phenylboronic acid and
4-substituted chlorobenzenes to test the obtained ligands 2
in the Suzuki reaction. The products were obtained in 19–
87% yields using 1 mol % catalyst loading (Table 2). The
effect of reaction time was also tested in the reaction of
4-chloroacetophenone and phenylboronic acid using
Pd(OAc)2/2e catalytic system and Cs2CO3 as a base (Table 2,
entries 12, 14). As seen from Table 2, we did not obtain
noteworthy yield of the desired product in 30 min (entry 14). In
the case of unsubstituted and 4-methoxy-substituted phenyl
chlorides the yields of the corresponding biaryl product
were in a range of 19–45% (entries 5–8, 15–17). In the case
of 4-chlorobenzaldehyde and 4-chloroacetophenone, the yields
were in a range of 64–79% and 74–87%, respectively. For
these results, we can argue, that the electron-withdrawing
groups attached to the aryl chloride increase yields, at the
same time electron-donating groups decrease yields. As it
is seen from Tables 1 and 2, perimidinium salts 2a–c give
comparable yields of the desired products, while ligand
precursor 2e is slightly more active than other ligands,
particularly for the Heck reaction. Compound 2e has
electron-donating methoxy groups on the benzyl
substituent attached to the perimidine nitrogen atom, and
possible explanation for the higher activity associated with
the electron-donating groups could be the higher basicity of
the coordinating carbon atom.
and 4-substitued chlorobenzene derivatives in the presence
of Pd(OAc)2–perimidinium salt system*
4-R2C6H4Cl
R2
Pd(OAc)2, 2a–c,e
B(OH)2
Cs2CO3
DMF, H2O
90°C, 4 h
Entry
R2
Perimidinium salt
Yield**, %
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
CHO
CHO
CHO
CHO
H
H
H
H
COMe
COMe
COMe
COMe
COMe
COMe
OMe
OMe
OMe
79
75
73
64
42
30
45
28
83
74
85
87
<10***
<10*4
20
19
25
2a
2b
2c
2e
2a
2b
2c
2e
2a
2b
2c
2e
2e
2e
2a
2b
2c
* Load of the reagents: phenylboronic acid (1.5 mmol), 4-RC6H4Cl
(1 mmol), Cs2CO3 (2 mmol), salt 2a–c,e (2 mol %), Pd(OAc)2 (1 mol %),
DMF (2 ml), H2O (2 ml).
** Yields are determined by GC and calculated based on amount of aryl
chloride.
*** t-BuOK is used as a base.
*4 Reaction time 30 min.
In summary, five novel 3-benzyl-1-(3-methylbenzyl)-
perimidinium salts were synthesized by the reaction of
N-(3-methylbenzyl)perimidine and substituted benzyl
chlorides under microwave irradiation. The synthesized
perimidinium salts were used as carbene precursors in the
Pd-catalyzed Heck and Suzuki reactions. We obtained 70–97%
yields for the Heck reaction and 19–87% yields for the
Suzuki reactions in aqueous media. This study is the first
report to employ a perimidine-based catalytic system in
water-containing media in literature thus far.
Experimental
FT-IR spectra were recorded on an ATR unit in the
range of 400–4000 cm–1 on a Perkin Elmer Spectrum 100
spectrophotometer. 1H and 13C NMR spectra were recorded
on a Bruker AC300P FT spectrometer (300 and 75 MHz,
respectively) in CDCl3, internal standard – TMS. Elemental
analyses were performed by a LECO CHNS-932 elemental
analyzer at IBTAM (Inonu University Scientific and
Technological Research Central). Melting points were
determined by an Electrothermal 9200 apparatus. All
reactions were performed in air. Compounds 1 and 2a–e were
synthesized in a CEM Discover System microwave reactor.
All catalytic reactions were monitored on an Agilent 6890 N GC
565

Chemistry of Heterocyclic Compounds 2015, 51(6), 563–567
system by GC-FID with HP-5 column (30 m×0.32 mm,
δ, ppm: 10.30 (1H, s, H-2); 7.47–6.74 (12H, m, H Ar); 5.46
(2H, s, CH2Ar); 5.42 (2H, s, CH2Ar); 2.50 (6H, s, 2',6'-CH3); 2.35
(3H, s, CH3); 2.29 (3H, s, CH3). 13C NMR spectrum, δ, ppm:
153.6; 139.2; 137.4; 134.9; 132.1; 131.8; 131.7; 130.5; 129.7;
129.2; 128.2; 128.1; 124.8; 124.6; 124.4; 124.1; 108.7; 108.1;
55.4; 51.8; 21.4; 20.7; 20.1. Found, %: C 78.64; H 6.72;
N 6.24. C29H29ClN2. Calculated, %: C 78.98; H 6.63; N 6.35.
1-(3-Methylbenzyl)-3-(2,3,4,5,6-pentamethylbenzyl)-
perimidinium chloride (2d). Yield 91%, white solid, mp
0.25 μM film thickness). Column chromatography was
performed using silica gel 60 (Sigma Aldrich).
Chemicals were purchased from Sigma Aldrich.
1H-Perimidine, 2-methylbenzyl chloride, 3-methylbenzyl
chloride, 4-methylbenzyl chloride, 2,4,6-trimethylbenzyl
chloride, 2,3,4,5,6-pentamethylbenzyl chloride, 3,4,5-tri-
methoxybenzyl chloride were used without additional
purification. Solvents were dried by standard methods.
1-(3-Methylbenzyl)perimidine (1). Perimidine (0.49 g,
2.9 mmol) was dissolved in distilled DMSO (10 ml);
t-BuOK (0.34 g, 3 mmol) was added into the solution, and
the mixture was stirred at ambient temperature for 30 min.
After this period, 3-methylbenzyl chloride (0.4 ml,
2.9 mmol) was added, and the mixture was irradiated by
MW at 110°C for 30 min. The progress of the reaction was
controlled by TLC (eluent EtOAc–hexane, 2:1). The
solvent and all volatile components were evaporated under
reduced pressure. The crude product was purified by
column chromatography (eluent EtOAc–hexane, 2:1).
Yield 0.74 g (95%), yellow solid, mp 154–157°C.
1
222–224°C. IR spectrum, ν, cm–1: 1659 (C=N). H NMR
spectrum, δ, ppm: 8.47 (1H, s, H-2); 7.64–6.95 (10H, m,
H Ar); 5.33 (2H, s, CH2Ar); 5.14 (2H, s, CH2Ar); 2.29 (6H,
s, 2CH3); 2.27 (3H, s, CH3); 2.26 (3H, s, CH3); 2.22 (6H,
s, 2CH3). 13C NMR spectrum, δ, ppm: 150.9; 139.2; 137.4;
134.9; 134.0; 133.7; 132.5; 131.2; 132.1; 129.6; 129.1;
128.8; 128.3; 128.1; 125.2; 124.6; 124.3; 123.2; 121.4;
108.8; 107.6; 55.6; 51.4; 21.3; 17.3; 17.2; 17.0. Found, %:
C 79.10; H 7.39; N 5.81. C31H33ClN2. Calculated, %:
C 79.38; H 7.09; N 5.97.
3-(3,4,5-Trimethoxybenzyl)-1-(3-methylbenzyl)perimi-
dinium chloride (2e). Yield 86%, white solid, mp 164–
166°C. IR spectrum, ν, cm–1: 1657 (C=N). 1H NMR
spectrum, δ, ppm: 11.50 (1H, s, H-2); 7.46–6.79 (12H, m,
H Ar); 5.63 (2H, s, CH2Ar); 5.50 (2H, s, CH2Ar); 3.89 (3H, s,
4'-OCH3); 3.83 (6H, s, 3',5'-OCH3); 2.33 (3H, s, ArCH3).
13C NMR spectrum, δ, ppm: 154.6; 153.9; 139.3; 138.5;
135.0; 131.8; 131.5; 131.1; 129.8; 129.2; 128.1; 128.0;
127.9; 127.5; 124.6; 124.5; 124.3; 121.9; 109.1; 108.9; 105.3;
60.8; 56.6; 55.4; 55.3; 21.4. Found, %: C 71.55; H 5.70;
N 5.75. C29H29ClN2O3. Calculated, %:C 71.23; H 5.98; N 5.73.
Pd-Catalyzed Heck reaction (General method). The
mixture of substituted aryl bromide (1.0 mmol), styrene
(156 mg, 1.5 mmol), perimidinium salt 2a–e (2 mol %),
Pd(OAc)2 (2.3 mg, 1 mol %), and Cs2CO3 (650 mg, 2.0 mmol)
was dissolved in 4 ml of DMF–H2O mixture, 1:1, and
stirred at 90°C for 4 h. Then the mixture was cooled to
ambient temperature and extracted by EtOAc. The organic
layer was separated and evaporated under reduced pressure.
The crude product was dissolved in EtOAc–hexane (1:5)
mixture, dried over MgSO4, filtered through a mini silica
column and analyzed by GC.17,19 All the stilbenes prepared
are known compounds, their physicochemical and spectral
characteristics correspond to the literature data.8,9
Pd-Catalyzed Suzuki reaction (General method). The
mixture of substituted aryl chloride (1.0 mmol), phenyl-
boronic acid (180 mg, 1.5 mmol), perimidinium salt 2a–e
(2 mol %), Pd(OAc)2 (2.3 mg, 1 mol %), and Cs2CO3
(650 mg, 2 mmol) was dissolved in 4 ml of DMF–H2O
mixture, 1:1, and stirred at 90°C for 4 h. Then the mixture
was cooled to ambient temperature, extracted with CH2Cl2.
The organic layer was separated and dried over MgSO4,
filtered through a mini silica column and analyzed by GC.
All the biaryls prepared are known compounds, their
physicochemical and spectral characteristics correspond to
the literature data.8,9
1
IR spectrum, ν, cm–1: 1629 (C=N). H NMR spectrum,
δ, ppm: 7.41–6.89 (10H, m, H Ar); 6.00 (1H, s, H-2); 4.72
(2H, s, CH2Ar); 2.36 (3H, s, CH3). 13C NMR spectrum,
δ, ppm: 148.8; 142.8; 139.0; 137.5; 135.4; 134.3; 129.0;
128.8; 128.7; 127.3; 127.0; 123.6; 123.1; 120.6; 119.7;
115.3; 102.1; 52.7; 21.4. Found, %: C 83.94; H 5.75;
N 10.45. C19H16N2. Calculated, %: C 83.79; H 5.92; N 10.29.
Synthesis of perimidinium salts 2a–e (General method).
1-(3-Methylbenzyl)perimidine (1) (0.98 g, 3.6 mmol) was
dissolved in dry DMF (1 ml), corresponding alkyl chloride
(3.6 mmol) was added into the solution and the mixture
was irradiated by MW at 110°C for 30 min. Then DMF
was evaporated under reduced pressure, and the crude
product was recrystallized from EtOH–Et2O mixture.
1-(3-Methylbenzyl)-3-(2-methylbenzyl)perimidinium
chloride (2a). Yield 82%, white solid, mp 217–220°C.
1
IR spectrum, ν, cm–1: 1657 (C=N). H NMR spectrum,
δ, ppm: 11.44 (1H, s, H-2); 7.74–6.54 (14H, m, H Ar); 5.70
(2H, s, CH2Ar); 5.60 (2H, s, CH2Ar); 2.51 (3H, s, CH3);
2.35 (3H, s, CH3). 13C NMR spectrum, δ, ppm: 154.9;
139.3; 135.8; 134.9; 131.7; 131.5; 131.4; 131.3; 129.7;
129.6; 129.2; 128.5; 128.1; 127.8; 126.6; 125.1; 124.6;
124.5; 124.4; 121.7; 109.1; 108.9; 55.4; 53.4; 21.4; 19.5.
Found, %: C 78.39; H 6.21; N 6.88. C27H25ClN2.
Calculated, %: C 78.53; H 6.10; N 6.78.
1-(3-Methylbenzyl)-3-(4-methylbenzyl)perimidinium
chloride (2b). Yield 96%, white solid, mp 227–230°C.
1
IR spectrum, ν, cm–1: 1667 (C=N). H NMR spectrum,
δ, ppm: 11.65 (1H, s, H-2); 7.45–6.83 (14H, m, H Ar); 5.56
(4H, s, 2CH2Ar); 2.36 (3H, s, CH3); 2.34 (3H, s, CH3).
13C NMR spectrum, δ, ppm: 154.7; 139.2; 138.9; 135.0;
131.8; 131.5; 131.4; 130.1; 129.7; 129.2; 128.7; 128.0;
127.8; 127.4; 124.4; 124.3; 121.9; 109.0; 55.3; 55.1; 22.1;
21.4. Found, %: C 78.20; H 6.20; N 6.61. C27H25ClN2.
Calculated, %: C 78.53; H 6.10; N 6.78.
1-(3-Methylbenzyl)-3-(2,4,6-trimethylbenzyl)perimidinium
chloride (2c). Yield 90%, white solid, mp 242–244°C.
Supplementary information to this article containing
1H and 13C NMR spectra of compounds 1, 2a–e is available
for authorized users.
1
IR spectrum, ν, cm–1: 1656 (C=N). H NMR spectrum,
566

Chemistry of Heterocyclic Compounds 2015, 51(6), 563–567
19. Gulcemal, S.; Kahraman, S.; Daran, J. C.; Cetinkaya, E.;
References
Cetinkaya, B. J. Organomet. Chem. 2009, 694, 3580.
20. Bazinet, P.; Yap, G. P. A.; Richeson D. S. J. Am. Chem. Soc.
2003, 125, 13314.
21. Alici, B.; Ozdemir, I.; Karaaslan, K.; Çetinkaya, E.;
Cetinkaya, B. J. Mol. Catal. A: Chem. 2005, 231, 261.
22. Ozdemir, I.; Alici, B.; Gurbuz, N.; Cetinkaya, B.; Çetinkaya E.
Russ. J. Coord. Chem. 2005, 31, 142.
23. Tu, T.; Malineni, J.; Bao, X.; Dötz, K. H. Adv. Synth. Catal.
2009, 351, 1029.
24. Tsurugi, H.; Fujita, S.; Choi, G.; Yamagata, T.; Ito, S.;
Miyasaka, H.; Mashima, K. Organometallics 2010, 29, 4120.
25. Chou, C.-C.; Yang, C.-C.; Syu, H.-B.; Kuo, T.-S. J. Organomet.
Chem. 2013, 745-746, 387.
26 Arzu Akinci, P.; Gulcemal, S.; Kazheva, O. N.; Alexandrov, G. G.;
Dyachenko, O. A.; Cetinkaya, E.; Cetinkaya B. J. Organomet.
Chem. 2014, 765, 23.
27. Bassyouni, F. A.; Abu-Bakr, S. M.; Hegab, K. H.; El-Eraky, W.;
El Beih, A. A.; Abdel Rehim, M. E. Res. Chem. Intermed.
2012, 38, 1527.
28. Azam, M.; Warad, I.; Al-Resayes, S.; Zahin, M.; Ahmad, I.;
Shakir, M. Z. Anorg. Allg. Chem. 2012, 638, 881.
29. Azam, M.; Warad, I.; Al-Resayes, S. I.; Alzaqri, N.; Khan, M. R.;
Pallepogu, R.; Dwivedi, S.; Musarrat, J.; Shakir, M. J. Mol.
Struct. 2013, 1047, 48.
1. Mizoroki, T.; Mori, K.; Ozaki, A. Bull. Chem. Soc. Jpn. 1971,
44, 581.
2. Heck, R. F.; Nolley, J. P. J. Org. Chem. 1972, 37, 2320.
3. Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979,
20, 3437.
4. Beletskaya, I. P.; Cheprakov, A. Chem. Rev. 2000, 100, 3009.
5. Kotha, S.; Lahiri, K.; Kashinath, D. Tetrahedron 2002, 58, 9633.
6. Phan, N. T. S.; Van Der Sluys, M.; Jones, C. W. Adv. Synth.
Catal. 2006, 348, 609.
7. Fortman, G. C.; Nolan, S. P. Chem. Soc. Rev. 2011, 40, 5151.
8. Kovala-Demertzi, D.; Kourkoumelis, N.; Derlat, K.;
Michalak, J.; Andreadaki, F. J.; Kostas, I. D. Inorg. Chim.
Acta 2008, 361, 1562.
9. An der Heiden, M.; Plenio, H. Chem.–Eur. J. 2004, 10, 1789.
10. Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008, 41, 1461.
11. Zhou, Z.; Liu, M.; Wu, X.; Yu, H.; Xu, G.; Xie, Y. Appl.
Organomet. Chem. 2013, 27, 562.
12. Sierra, D.; Bhuvanesh, N.; Reibenspies, J. H.; Gladysz, J. A.;
Klahn, A. H. J. Organomet. Chem. 2014, 749, 416.
13. Herrmann, W. A.; Elison, M.; Fischer, J.; Köcher, C.; Artus, G. R. J.
Angew. Chem., Int. Ed. 1995, 34, 2371.
14. Tang, Y.-Q.; Lu, J.-M.; Shao, L.-X. J. Organomet. Chem.
2011, 696, 3741.
15. Pavia, C.; Ballerini, E.; Bivona, L. A.; Giacalone, F.; Aprile, C.;
Vaccaro, L.; Gruttadauria, M. Adv. Synth. Catal. 2013, 355, 2007.
16. Ozdemir, I.; Yigit, M.; Cetinkaya, E.; Cetinkaya, B. Appl.
Organomet. Chem. 2006, 20, 187.
30. Chan, A. H.; Wereszczynski, J.; Amer, B. R.; Yi, S. W.;
Jung, M. E.; McCammon, J. A.; Clubb, R. T. Chem. Biol.
Drug Des. 2013, 82, 418.
31. Farghaly, T. A.; Mahmoud, H. K. Arch. Pharm. (Weinheim,
Ger.) 2013, 346, 392.
17. Demir, S.; Zengin, R.; Ozdemir, I. Heteroat. Chem. 2013, 24, 77.
18. Demir, S.; Ozdemir, I.; Cetinkaya, B. Appl. Organomet.
Chem. 2006, 20, 254.
32. Koca, I.; Ungoren, S. H.; Kibriz, I. E.; Yilmaz, F. Dyes Pigm.
2012, 95, 421.
567