Bis(imidazolium) chloride based on 1,2-phenylenediamine as efficient ligand precursor for palladium-catalyzed Mizoroki-Heck cross-coupling reaction

Article abstract of DOI:10.1016/j.jorganchem.2019.02.025

Bis(imidazolium) chlorides based on 1,2-phenylenediamine were introduced as efficient ligand precursors in the Pd-catalyzed Mizoroki-Heck cross-coupling reactions of substituted aryl halides with activated alkenes to afford the corresponding functionalized alkenes. While high to excellent yields (78–96%) were obtained with aryl bromides, moderate yields (51–59%) were achieved for aryl chlorides in this protocol.

Full text of DOI:10.1016/j.jorganchem.2019.02.025

Accepted Manuscript
Bis(imidazolium) chloride based on 1,2-phenylenediamine as efficient ligand
precursor for palladium-catalyzed Mizoroki-Heck cross-coupling reaction
Ahmad Takallou, Azizollah Habibi, Azim Ziyaei Halimehjani, Saeed Balalaie
PII:
S0022-328X(18)30979-3
DOI:
https://doi.org/10.1016/j.jorganchem.2019.02.025
JOM 20727
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 2 November 2018
Revised Date: 7 February 2019
Accepted Date: 27 February 2019
Please cite this article as: A. Takallou, A. Habibi, A.Z. Halimehjani, S. Balalaie, Bis(imidazolium) chloride
based on 1,2-phenylenediamine as efficient ligand precursor for palladium-catalyzed Mizoroki-Heck
cross-coupling reaction, Journal of Organometallic Chemistry (2019), doi: https://doi.org/10.1016/
j.jorganchem.2019.02.025.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Bis(imidazolium) chloride based on 1,2-phenylenediamine as efficient ligand precursor for
palladium-catalyzed Mizoroki-Heck cross-coupling reaction
Ahmad Takallou,a Azizollah Habibi,*a Azim Ziyaei Halimehjania and Saeed Balalaieb
a Faculty of Chemistry, Kharazmi University, No. 43. Mofateh Street, Enghelab Ave, P. Code
15719-14911, Tehran, Iran.*E-mail: habibi@khu.ac.ir
b Department of Chemistry, K. N. Toosi University of Technology, P. O. Box 15875 – 4416,
Tehran, Iran.
ABSTRACT
Bis(imidazolium) chlorides based on 1,2-phenylenediamine were introduced as efficient ligand
precursors in the Pd-catalyzed Mizoroki-Heck cross-coupling reactions of substituted aryl
halides with activated alkenes to afford the corresponding functionalized alkenes. While high to
excellent yields (78-96%) were obtained with aryl bromides, moderate yields (51-59%) were
achieved for aryl chlorides in this protocol.
Keywords: N-Heterocyclic carbene ligands, Mizoroki-Heck reaction, Aryl bromides, Terminal
alkenes, Palladium

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1. Introduction
Over the past few decades, palladium-catalyzed cross-coupling reactions have surprisingly
advanced a wide range of organic reactions [1]. Among them, the coupling reaction of aryl
halides with activated alkenes (Mizoroki-Heck coupling reaction) is one of the best synthetic
routes toward C-C bond formation [2]. Application of aryl iodides as highly efficient substrates
in the Mizoroki-Heck reaction has been limited due to their low availability and high cost. On
the other hand, strong bond between Csp2-Br and Csp2-Cl needs highly active catalysts for
activation to be applicable in coupling reactions [3]. The enormous applications of Mizoroki-
Heck reaction in the synthesis of novel materials, pharmaceuticals and natural products have
encouraged organic chemists to develop highly active catalysts and efficient synthetic methods
for this transformation [4].
A wide range of palladium catalysts and ligands have been developed for Mizoroki-Heck
reaction. Among them, phosphine-containing ligands have been extensively utilized in the
Mizoroki-Heck reaction to improve the catalytic activity of complexes via stabilization and
generation of Pd(0) species from Pd(II) complexes [5]. Unfortunately, phosphine ligands are
toxic, air and moisture sensitive, and highly expensive [6]. To overcome these limitations,
various catalytic systems have been introduced. Recently, various phosphine-free ligands
including oxazolines, N-heterocyclic carbenes (NHCs), diazacrown ethers, Schiff bases,
hydrazines, amino alcohols, amino acids and porphyrins have been established for Pd-catalyzed

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C-C cross-coupling reactions [7]. Between these ligands, in situ prepared N-heterocyclic
carbenes have been proven to be significant ligands for Pd-mediated cross-coupling reactions
[8]. Lately, NHCs have attracted more efforts for introducing more efficient ligands in this area.
Their advantages are easy preparation of NHCs on the large scale, their air-stability, and
generally similar or higher performance in comparison to phosphane-based systems. Also, the
stronger σ-donor and weaker π-acceptor properties of NHCs compared to phosphane ligands
cause higher electron density on the Pd (or any NHC-metal complexes) which increase their
stability to moisture, air, and heat [9]. Among NHC ligands, bis-NHC ligands containing an
alkyl, aryl, pyridyl, lutidinyl, cyclohexyl, polyether and a solid support as bridging linkers have
been well investigated for the synthesis of NHC-metal complexes with potential applications as
catalyst in synthetic organic chemistry [10]. Both pre-prepared and in situ prepared imidazolium
based NHC-Pd complexes are applied extensively for Mizoroki-Heck reaction. Deprotonation of
NHC salts with a base in the presence of a Pd precursor can furnish the corresponding palladium
complexes in situ suitable for cross-coupling reactions. In this regard, recently, Nadri et al.
reported the application of 1,1'-Methylene-3,3'-bis[(N-(tert-butyl)imidazol-2-ylidene] as efficient
ligand precursor for Pd-catalyzed C-C cross-coupling reaction of aryl bromides and activated
alkenes (Scheme 1a) [11]. In addition, bis-imidazolium ligand precursor in conjunction with
Pd(OAc)2 as catalyst for Suzuki-Miyaura reaction is developed by Rahimi and Schmidt (Scheme
1b) [12]. In this regard, here we are interested to report the preparation of four bis-imidazolium

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salts and their applications as ligand precursor for Pd-catalyzed Mizoroki-Heck cross-coupling
reaction of aryl bromides and chlorides with activated alkenes (Scheme 1c).
(a) Nadri et al [10]
Pd(OAc)2
Imidazolium salt
N
N
N+
N+
Ar
Ar-Br
+
R
R
2 Br-
1 eq. K2CO3
DMF, 135 oC, 1-7 h
(b) Rahimi and Schmidt [11]
Cl
Cl
Me
N
N
Pd(OAc)2
Imidazolium salt
NaOt-Bu
N+
Br
B(OH)2
Cl
Cl
-
2 BF4
+
N+
Toluene, rt
Me
(c) This work
O
N+
PdCl2
Imidazolium salt
Cs2CO3
Me
Me
NH
N
N
2Cl-
Ar
Ar-Br (Cl)
R
+
R
DMF, 125 oC
NH
N+
O
Scheme 1. Reported and proposed bis(imidazolium) salts as ligand precursor for C-C cross-coupling reactions.
2. Results and discussion
Four bis-imidazolium salts based on o-phenylenediamine as ligand precursor suitable for Pd-
catalyzed Mizoroki-Heck cross-coupling reactions were prepared. As shown in Scheme 2, the
reactions of chloroacetyl chloride with o-phenylenediamine and its derivatives were carried out

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to prepare the corresponding N,N'-(1,2-phenylene)bis(2-chloroacetamide) derivatives 1a-d
(yields (%): 1a; 96, 1b:93, 1c: 89, 1d: 91). Next, 1a-d reacted with an excess amount of 1-
methylimidazole to afford the corresponding bis-imidazolium salts 2a-d (yields (%): 2a; 74,
2b:79, 2c: 76, 2d: 75). The structures of 2a-d were characterized by IR, 1H and 13C NMR, mass
and elemental analysis.
Scheme 2. Synthetic route for preparation of bis-imidazole ligand precursor
After successful preparation of bis-imidazolium salts 2a-d, their applications as ligand precursor
in the Mizoroki-Heck reaction were investigated. At first, the model reaction between styrene
and bromobenzene was screened in the presence of Cs2CO3 (1.1 equiv) in various solvents such
as water, toluene, DMSO, dioxane, and DMF by using 1.1 mol % of PdCl2 at 120 °C (Table 1,
entries 1-5). The best yield was obtained in DMF. Next, the effect of catalyst loading was
examined. While by decreasing the amount of the catalyst loading to 0.8 mol %, the yield was
decreased to 85%, no improvement in reaction yield was observed using 1.7 mol% of the catalyst
(Table 1, entries 6-7). In addition, by decreasing of the reaction temperature to 80 °C, the yield
was significantly dropped to 38% (Table 1, entry 8). The best yield (96%) was obtained at 125

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°C (Table 1, entry 10). By performing the model reaction in the presence of various bases such
as Et3N, DIPEA (N,N-diisopropylethylamine), t-BuOK, NaOH, and K2CO3 instead of Cs2CO3
under optimized reaction conditions, lower yields were obtained (Table 1, entries 11-15). By
using bis-imidazolium salts 2b-d as ligand precursor, the reaction yields were slightly decreased
(about 1-3%) under optimized reaction conditions (Table 1, entries 16-18]. It may be attributed
to the higher electron density on the nitrogens of the amide groups in 2a and improvement of the
catalyst activity toward the Mizoroki-Heck coupling reaction. In addition, to confirm the
efficiency of the bis(imidazolium) salts as ligand precursor in the proposed typical reaction, we
performed the reaction under ligand- free condition and low yield of the product 5a was resulted
(Table 1, entry 19). Furthermore, when 1a-d was used as ligand precursor instead of 2a-d, the
yields were significantly decreased even by prolonging the reaction time to 24 h (Table 1, entries
20-23]. Finally, stirring a solution of styrene (1.2 equiv) and bromobenzene (1 equiv) in the
presence of Cs2CO3 (1.1 equiv), PdCl2 (1.1 mol %), and 2a (1.1 mol %) in DMF at 125 °C was
considered as optimal reaction conditions for further derivatization.
<<Table 1>>
In order to explore the scope of the reaction, various activated and non-activated aryl halides
and terminal olefins were applied in this protocol (Table 2). It is conceivable that the reaction of
2a with Cs2CO3 produces the corresponding NHC ligand in situ for generation of the active

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catalyst with PdCl2 suitable for activation of the starting materials toward cross-coupling
reaction. Several aryl bromides bearing electron-withdrawing and electron-donating groups were
applied successfully in cross-coupling reaction to afford the corresponding trans isomer 5.
Lower yields were obtained for aryl bromides containing a substituent on the ortho position
compare to meta and para positions. The results showed that aryl bromides are more reactive
than aryl chlorides in the reaction with styrene, methyl acrylate and ethyl acrylate. For this
purpose, the chemoselectivity of the catalytic system was examined using 4-chloro-1-
bromobenzene and 4-fluoro-1-bromobenzene (Table 2, entries 9-10 and 12-14). This study
showed that, -Br is a better leaving group than –Cl and –F, and the cross-coupling reaction was
preferably occurred in the bromide position. Although chlorobenzene gave 51% and 55% yield
in the reaction with styrene and methyl acrylate respectively. Using an electron-withdrawing
group on the phenyl ring such as 4-nitro-1-chlorobenzene improved the yield up to 59% [Table
2, entry 17].
<<Table 2>>
The catalytic efficiency of our catalyst in Mizoroki–Heck cross-coupling reaction of
bromobenzene and styrene is compared with those reported in the literatures and summarized in
Table 3. As revealed from Table 3, our catalyst shows good activity in comparison to some of
the reported methods in literatures.

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<<Table 3>>
3. Conclusions
In conclusion, a new catalytic system for the Mirozoki-Heck cross coupling reactions of
aryl bromides and chlorides with activated olefins is reported using a new category of
bis(imidazolium) chlorides based on 1,2-phenylenediamine as ligand precursor, Cs2CO3
and PdCl2. The advantages of this method include moderate to excellent yields, simple
synthesis of ligand precursor, excellent regioselectivity for aryl bromides in the presence
of aryl chlorides and fluorides.
4. Experimental
4.1. General: All materials were purchased from Merck, Aldrich, and Fluka, and used as
received. Melting points were measured by an Electrothermal 9100 apparatus and are
uncorrected. FT-IR spectra was recorded on a Perkin-Elmer 843 spectrophotometer using KBr
disc. NMR spectra were recorded on a Bruker Avance 300 MHz using DMSO-d6 as solvent and
Me4Si (TMS) as internal standard at 298 K. The chemical shifts (δ) are reported in parts per
million (ppm) and coupling constants (J) are given in Hz. Low resolution mass spectra was
collected on a Hewlett-Packard 5973 mass spectrometer operating at 70 eV. Elemental analyses
were carried out on a Perkin-Elmer 2004 series [II] CHN elemental analyzer.

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4.2. General Procedure for the Preparation of 2a-d:
To a solution of 1,2-phenylenediamine (or its derivatives) (10.0 mmol) in CH2Cl2 (30 mL),
aqueous NaOH (20.0 mmol in 8 mL water) was added. Then, chloroacetyl chloride solution (2.8
g, 25.0 mmol in 25 mL CH2Cl2) was added to the reaction mixture via dropping funnel with
stirring. The mixture was further stirred for 20 min to afford a precipitate. The solid was filtered
off, washed with ether (10 mL), and dried under vacuum to afford 1a-d [yields (%): 1a; 96,
1b:93, 1c: 89, 1d: 91]. The solids were used in the next step without further purification. Then,
1-methylimidazole (1.8 g, 22 mmol) was added to a solution of 1a-d (in 40 mL DMF). The
reaction mixture was stirred for 10 h at 85 °C. Then, the mixture was cooled to room temperature
and the solvent was removed under vacuum and the resulting solid was suspended in 30 mL
acetone with stirring for 15 min. Finally, the suspension was filtered and dried in vacuum to give
the pure product. (Yields (%): 2a; 74, 2b:79, 2c: 76, 2d: 75).
4.3. Characterization data for 2a-2d:
3,3'-(((4,5-dimethyl-1,2-phenylene)bis(azanediyl))bis(2-oxoethane-2,1-diyl))bis(1-methyl-
1H-imidazol-3-ium) Chloride (2a):
Yield: 3.35 g (74%); yellow solid; 1H NMR (300 MHz, DMSO-d6) δ 10.53 (s, 2H), 9.31 (s, 2H),
7.86 (m, 2H), 7.72 (m, 2H), 7.37 (s, 2H), 5.42 (s, 4H), 3.91 (s, 6H), 2.16 (s, 6H) ppm; 13C NMR
(75 MHz, DMSO-d6) δ 163.8, 137.5, 132.8, 126.9, 125.1, 123.4, 122.7, 51.0, 35.5, 18.7 ppm.
Anal. calcd for C20H26Cl2N6O2 (%): C, 52.99; H, 5.78; N, 18.54. Found (%): 51.83; H, 5.48; N,
18.17; IR (cm-1): 3082, 2974, 1688, 1597, 1552, 1496, 1441, 1342, 1301, 1250, 1179, 1107, 750, 692,
619, 501; LRMS (EI) [M – Cl]+ m/z 382.

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3,3'-(((4-methyl-1,2-phenylene)bis(azanediyl))bis(2-oxoethane-2,1-diyl))bis(1-methyl-1H-
imidazol-3-ium) Chloride (2b):
Yield: 3.46 g (79%); pale yellow solid; mp 225-227 °C; 1H NMR (300 MHz, DMSO-d6) δ 10.67
(s, 1H), 10.62 (s, 1H), 9.35 (s, 2H), 7.88 (m, 2H), 7.74 (m, 2H), 7.49 – 7.35 (m, 2H), 6.97 (m,
1H), 5.46 (s, 2H), 5.44 (s, 2H), 3.91 (s, 6H), 2.24 (s, 3H) ppm; 13C NMR (75 MHz, DMSO-d6) δ
164.2, 137.8, 134.4, 129.6, 127.1, 124.6, 123.7, 123.0, 51.3, 35.8, 20.6 ppm; Anal. calcd for
C19H24Cl2N6O2 (%): C, 51.94; H, 5.51; N, 19.13. Found (%): C, 51.76; H, 5.62; N, 19.16; IR
(cm-1): 2977, 1687, 1606, 1549, 1511, 1309, 1251, 1179, 1107, 821, 748; LRMS (EI) [M – Cl]+
m/z 368.
3,3'-(((4-chloro-1,2-phenylene)bis(azanediyl))bis(2-oxoethane-2,1-diyl))bis(1-methyl-1H-
imidazol-3-ium) Chloride (2c):
Yield: 3.48 g (76%); pale yellow, 1H NMR (300 MHz, DMSO-d6)
δ 10.97 (s, 1H), 10.88 (s, 1H), 9.36 (s,
1H), 9.35 (s, 1H), 7.89 (m, 2H), 7.74 (m, 3H), 7.64 – 7.52 (m, 1H), 7.23 (dd, J = 8.7, 2.5 Hz, 1H), 5.49 (s,
2H), 5.48 (s, 2H), 3.91 (s, 6H) ppm; 13C NMR (75 MHz, DMSO-d6)
δ
164.7, 164.5, 137.8, 131.2, 128.7,
128.2, 123.8, 123.1, 120.5, 51.4, 35.8 ppm; Anal. calcd for C18H21Cl3N6O2 (%): C, 47.02; H, 4.60; N,
18.28. Found (%): C, 47.21; H, 4.44; N, 18.61; IR (cm-1): 2952, 1694, 1612, 1546, 1487, 1396, 1306,
1250, 1180, 830; LRMS (EI) [M – Cl]+ m/z 388.
3,3'-((1,2-phenylenebis(azanediyl))bis(2-oxoethane-2,1-diyl))bis(1-methyl-1H-imidazol-3-
ium) Chloride (2d):
1
Yield: 3.18 g (75%); pink solid; H NMR (300 MHz, DMSO-d6) δ 10.74 (s, 1H), 9.36 (s, 1H),
7.89 (d, J = 1.7 Hz, 1H), 7.74 (d, J = 1.7 Hz, 1H), 7.59 (dd, J = 6.0, 3.6 Hz, 1H), 7.16 (dd, J =
13
6.1, 3.5 Hz, 1H), 5.48 (s, 2H), 3.91 (s, 3H) ppm; C NMR (75 MHz, DMSO-d6) δ 164.3, 137.8,

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129.7, 125.2, 124.7, 123.7, 123.0, 51.4, 35.8 ppm; Anal. calcd for C18H22Cl2N6O2 (%): C, 50.83;
H, 5.21; N, 19.76. Found (%): C, 51.03; H, 5.33; N, 19.14. IR (cm-1): 2955, 1688, 1597, 1551,
1496, 1442, 1341, 1310, 1250, 1179, 1107, 751, 693, 618, 502; LRMS (EI) [M – Cl]+ m/z 354.
4.4. General Procedure for the Mizoroki–Heck Cross Coupling Reaction:
In a Schlenk flask under N2 atmosphere, 2a (5 mg, 0.011 mmol), PdCl2 (2 mg ,0.011 mmol),
Cs2CO3 (358 mg, 1,1 mmol) and DMF (1.5 mL) were added. The reaction mixture was heated at
90 °C for 30 min. Then, an aryl halide (1.0 mmol) and an olefin (1.2 mmol) were added and the
mixture was further stirred at 125 °C under air atmosphere conditions. The reaction progress was
monitored by Thin Layer Chromatography (EtOAc/hexane, 1:9). After completion of the
reaction, the mixture was cooled to room temperature, and water (8 mL) was added and was
extracted with EtOAc (3 × 10 mL). The organic solvent was dried over Na2SO4 and was
evaporated under vacuum to give the crude product which was further purified by column
chromatography using EtOAc/hexane, 1:9.
4.5. 1HNMR data of Mizoroki-Heck products (5a-5o):
(E)-1,2-diphenylethene (5a): 1H NMR (300 MHz, Chloroform-d) δ 7.54 (m, 4H), 7.38 (m,
5H), 7.32 – 7.25 (m, 3H).
Methyl cinnamate (5b): 1H NMR (300 MHz, Chloroform-d) δ 7.70 (d, J = 16.0 Hz, 1H), 7.51
(m, J = 3.9, 1.6 Hz, 2H), 7.43 – 7.32 (m, 3H), 6.44 (d, J = 16.0 Hz, 1H), 3.80 (s, 3H).
(E)-1-styrylnaphthalene (5c): 1H NMR (300 MHz, Chloroform-d) δ 8.39 – 8.29 (m, 1H), 8.10
– 7.79 (m, 4H), 7.76 – 7.55 (m, 5H), 7.54 – 7.33 (m, 3H), 7.31 – 7.17 (m, 1H).

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Ethyl (E)-3-(naphthalen-1-yl)acrylate (5d): 1H NMR (300 MHz, Chloroform-d) δ 8.54 (d, J =
15.7 Hz, 1H), 8.21 (dd, J = 8.4, 1.4 Hz, 1H), 7.97 – 7.82 (m, 2H), 7.76 (dd, J = 7.2, 1.1 Hz, 1H),
7.63 – 7.38 (m, 3H), 6.54 (d, J = 15.8 Hz, 1H), 4.33 (q, J = 7.1 Hz, 2H), 1.39 (t, J = 7.1 Hz, 3H).
(E)-1-bromo-4-styrylbenzene (5e): 1H NMR (300 MHz, Chloroform-d) δ 7.54 – 7.48 (m, 2H),
7.45 – 7.26 (m, 5H), 7.17 (m, 1H).
Methyl (E)-3-(4-bromophenyl)acrylate (5f) :1H NMR (300 MHz, Chloroform-d) δ 7.60 (d, J =
16.0 Hz, 1H), 7.50 (d, J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 6.41 (d, J = 16.0 Hz, 1H), 3.79
(s, 3H).
(E)-1-methyl-3-styrylbenzene (5g): 1H NMR (300 MHz, Chloroform-d) δ 7.54 – 7.46 (m, 3H),
7.42 – 7.27 (m, 6H), 7.14 – 6.91 (m, 2H), 2.89 (s, 3H).
Methyl (E)-3-(m-tolyl)acrylate (5h): 1H NMR (300 MHz, Chloroform-d) δ 7.67 (d, J = 16.0
Hz, 1H), 7.39 – 7.16 (m, 4H), 6.43 (d, J = 16.0 Hz, 1H), 3.80 (s, 3H), 2.37 (s, 3H).
Methyl (E)-3-(2-chlorophenyl)acrylate (5i): 1H NMR (300 MHz, Chloroform-d) δ 8.07 (d, J =
16.0, 1H), 7.63 – 7.54 (m, 1H), 7.38 (m, 1H), 7.31 – 7.20 (m, 2H), 6.41 (d, J = 16.0, 1H), 3.80 (s,
3H).
Ethyl (E)-3-(2-chlorophenyl)acrylate(5j):1H NMR (300 MHz, Chloroform-d) δ 7.60 (d, J =
16.0 Hz, 1H), 7.53 – 7.47 (m, 2H), 7.39 – 7.33 (m, 2H), 6.41 (d, J = 16.0 Hz, 1H), 3.79 (s, 3H).
Methyl (E)-3-(2-ethylphenyl)acrylate (5k): 1H NMR (300 MHz, Chloroform-d) δ 8.04 (d, J =
15.8 Hz, 1H), 7.56 (d, J = 7.4 Hz, 1H), 7.39 – 7.28 (m, 1H), 7.25 – 7.17 (m, 2H), 6.38 (d, J =
15.8 Hz, 1H), 3.82 (s, 3H), 2.79 (q, J = 7.6 Hz, 2H), 1.23 (t, J = 7.6 Hz, 3H).
Methyl (E)-3-(2-fluorophenyl)acrylate(5l): 1H NMR (300 MHz, Chloroform-d) δ 7.82 (d, J =
16.2 Hz, 1H), 7.53 (td, J = 7.6, 1.8 Hz, 1H), 7.41 – 7.20 (m, 1H), 7.20 – 6.97 (m, 2H), 6.54 (d, J
= 16.3 Hz, 1H), 3.81 (s, 3H).

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Methyl (E)-3-(4-fluorophenyl)acrylate (5m): 1H NMR (300 MHz, Chloroform-d) δ 7.63 (d, J =
16.0 Hz, 1H), 7.53 – 7.42 (m, 2H), 7.05 (t, J = 8.6 Hz, 2H), 6.34 (d, J = 16.0 Hz, 1H), 3.78 (s,
3H).
Ethyl (E)-3-(4-fluorophenyl)acrylate (5n): 1H NMR (300 MHz, Chloroform-d) δ 7.65 (d, J =
16.0 Hz, 1H), 7.56 – 7.45 (m, 2H), 7.13 – 6.97 (m, 2H), 6.36 (d, J = 16.0 Hz, 1H), 4.26 (q, J =
7.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H).
Methyl (E)-3-(3-nitrophenyl)acrylate (5o): 1HNMR (300 MHz, Chloroform-d) δ 8.36 (t, J =
2.0 Hz, 1H), 8.22 (ddd, J = 8.2, 2.3, 1.1 Hz, 1H), 7.82 (dd, J = 7.8, 1.4 Hz, 1H), 7.75 – 7.68 (m,
1H), 7.58 (t, J = 8.0 Hz, 1H), 6.56 (d, J = 16.0 Hz, 1H), 3.83 (s, 3H).
Acknowledgements
We are sincerely thank to Kharazmi University Vice-President of Research and
Technology for financial support.
References
[1] (a) K. Muniz, Angew. Chem. Int. Ed. 48 (2009) 9412-9423. (b) H. C. Shen, Y. F. Wu,
Y. Zhang, L. F. Fan, Z.Y. Han, L. Z. Gong, B, Angew. Chem. Int. Ed. 57 (2018) 2372-
2376. (c) B. Movassagh, A. Takallou, A. Mobaraki, J. Mol. Catal. A: Chem. 15 (2015)
55-65. (d) B. P. Fors, S. L. Buchwald, J. Am. Chem. Soc. 132 (2010) 15914-15917. (e)
P. Ruiz-Castillo, D. G. Blackmond, S. L. Buchwald, J. Am. Chem. Soc. 137 (2015)
3085-3092. (f) X. B. Lan, Y. Li, Y. F. Li, D. S. Shen, Z. Ke, F. S. Liu, J. Org. Chem,

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82 (2017) 2914-2925. (g) N. Singh, R. Singh, D. S. Raghuvanshi, K. N. Singh, Org.
Lett. 15 (2013) 5874-5877.
[2]
(a) M. L. Kantam, P. Srinivas, J. Yadav, P. R. Likhar, S. Bhargava, J. Org. Chem.
74 (2009) 4882-4885. (b) W. B. Reid, J. J. Spillane, S. B. Krause, D. A. Watson, J.
Am. Chem. Soc. 138 (2016) 5539-5542. (c) C. Wu, J. Zhou, J. Am. Chem. Soc. 136
(2014) 650-652.
[3]
B. M. Partridge, J. F. Hartwig, Org. Lett. 15
(a) Y. H. Ding, H. X. Fan, J. Long, Q. Zhang, Y. Chen, Bioorganic Med. Chem.
Lett. 13 2013) 6087-6092. (b) A. B. Dounay, L. E. Overman, Chem Rev. 103 2003)
2945-2964.
[5] C. C. C. J. Seechurn, T. Sperger, T. G. Scrase, F. Schoenebeck, T. J. Colacot, J.
Am. Chem. Soc. 139 2017) 5194-5200.
[6] P. Zhou, Y. Li, P. Sun, J. Zhou, J. Bao, Chem. Commun. 14 (2007) 1418-1420.
(2013) 140-143.
[4]
(
(
(
[7] (a) Y. Mata, M. Dieguez, O. Pamies, C. Claver, Org. Lett. 7 (2005) 5597-5599. (b) B.
Karimi, D. Enders, Org. Lett. 8 (2006) 1237-1240. (c) B. Movassagh, S.Yasham, M.
Navidi, Synlett 24
Organometal. Chem. 29
R. Fernandez, J. M. Lassaletta, Org. Lett. 17
Matousek, T. Mallat, A. Baiker, Chem. Eur. J. 14 (2008) 2699-2708. (g) R. E. Plata,
(
2013) 2671-2674. (d) M. Keles, H. Keleş, D. M. Emir, Appl.
2015) 543-548. (e) Y. Álvarez-Casao, D. Monge, E. Álvarez,
2015) 5104-5107. (f) P. Kukula, V.
(
(

ACCEPTED MANUSCRIPT
D. E. Hill, B. E. Haines, D. G. Musaev, L. Chu, D. P. Hickey, M. S. Sigman, J. Q. Yu,
D. G. Blackmond, J. Am. Chem. Soc. 139
C. Lau, C. M. Che, Chem. Eur. J. 19 2013) 5654-5664.
[8] D. J. Müller, C. Schlepphorst, F. Glorius, Chem. Soc. Rev. 46
[9] (a) C. Gibard, H. Ibrahim, A. Gautier, F. Cisnetti, Organometallics. 32
4283. (b) F. Nahra, S. R. Patrick, A. Collado, S. P. Nolan, Polyhedron. 84
62. (c) M. S. Viciu, R. M. Kissling, E. D. Stevens, S. P. Nolan, Org Lett. 4
(2017) 9238-9245. (h) W. P. To, Y. Liu, T.
(
(
2017) 4845-4854-.
2013) 4279-
2014) 59-
2002)
(
(
(
2229-2231. (d) D. Janssen-Müller, C. Schlepphorst, F. Glorius, Chem. Soc. Rev.
2017, 46, 4845-4854. (e) K. M. Hindi, M. J. Panzner, C. A. Tessier, C. L. Cannon, W.
J. Youngs, Chem Rev. 109 (2009) 3859-3884.
[10] (a) R. Zhong, A. C. Lindhorst, F. J. Groche, F. E. Kuhn, Chem. Rev. 117 (2017)
1970-2058. (b) L. Zhou, L. Wang, Synthesis (2006) 2649-2652.
[11] S. Nadri, E. Rafiee, S. Jamali, M. Joshaghani. Synlett 26
[12] A. Rahimi, A. Schmidt, Synlett 9 (2010) 1327-1330.
(2015) 619-624.
[13] (a) B. Movassagh, S. Ranjbari, Appl Organometal Chem. 32 (2018) 4224-4230.
(b) H. M. Savanur, R. G. Kalkhambkar, K. K. Laali, Appl. Catal., A. 543 (2017) 150-
161. (c) D. Khalili, A. R. Banazadeh, E. Etemadi Davan, Catal. Lett. 147 (2017) 2674-
2687. (d) B. Movassagh, F. S. Parvis, M. Navidi, Appl. Organometal. Chem. 29 (2015)
40–44.

ACCEPTED MANUSCRIPT
Table 1 Optimization of the reaction conditionsa

ACCEPTED MANUSCRIPT
PdCl2
T(°C)/Time (h)
Ligand precursor
(x mol%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2a (0.8%)
2a (1.7%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2a (1.1%)
2b (1.1%)
2c (1.1%)
2d (1.1%)
-
Entry
Solvent
Base
Yield b
(x mol %)
1
2
H2O
Toluene
DMSO
Dioxane
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Et3N
120/6
120/5
120/3
120/5
120/3
120/5
120/3
80/10
115/5
125/3
125/3
125/3
125/3
125/3
125/3
125/3
125/3
125/3
125/10
125/24
125/24
125/24
125/24
1.1
1.1
1.1
1.1
1.1
0.8
1.7
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1
15
38
66
52
93
85
93
38
72
96
77
71
78
75
80
92
90
90
25
18
22
17
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20h
21i
22j
23k
DIPEA
t-BuOK
NaOH
K2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
1.1
1.1
1.1
1.1
1a (1.1%)
1b (1.1%)
1c (1.1%)
1d (1.1%)
19
b
aReaction conditions: Bromobenzene (1mmol), Styrene (1.2 mmol), base (1.1 mmol), solvent (1.5 mL). Isolated
yields.
Table 2 ‘Diversity of Mizoroki-Heck reaction of Aryl halides and olefins.a

ACCEPTED MANUSCRIPT
Entry
1
ArX
PhBr
R1
Product
5a
Time (h)
Yieldsb
96
Ph
3
3.5
3
2
PhBr
CO2Me
Ph
5b
5c
95
3
1-NaphBr
1-NaphBr
4-BrC6H4Br
4-BrC6H4Br
3-MeC6H4Br
3-MeC6H4Br
2-ClC6H4Br
2-ClC6H4Br
2-EtC6H4Br
2-FC6H4Br
4-FC6H4Br
4-FC6H4Br
PhCl
95
4
CO2Et
Ph
4
93
5d
5e
5
3
94
6
CO2Me
Ph
3.5
3.5
3.5
5
95
5f
7
92
5g
8
CO2Me
CO2Me
CO2Et
CO2Me
CO2Me
CO2Me
CO2Et
Ph
5h
5i
93
9
84
10
11
12
13
14
15
16
17
5
85
5j
5.5
5
78
5k
5l
87
4.5
4.5
15
15
15
94
5m
5n
5a
91
51
PhCl
CO2Me
CO2Me
55
5b
5o
4-NO2C6H4Cl
59
a
Reaction conditions: Aryl halide (1 mmol), olefin (1.2 mmol), Cs2CO3 (1.1 mmol), DMF (1.5 mL), 125 °C, under
air. b Isolated yield.

ACCEPTED MANUSCRIPT
Table 3 Comparison of activity and reaction conditions for homogeneous and heterogeneous catalysts in the
Mizoroki-Heck reaction of bromobenzene and styrene.
Entry
Catalyst/(mol% Pd)
Solvent
Base
Time (h)/T (°C)
Yield (%)a
1
b2
3
2a, PdCl2 (1.1 mol%)
DMF
DMF
Cs2CO3 (1.1 mmol)
Et3N (1.1 mmol)
K3PO4 (2 mmol)
basic-IL (4 mmol)
Cs2CO3 (1.5 mmol)
Et3N (1.1 mmol)
3/125
0.17/130
16/130
4/70
96 [This work]
74 [13a]
PdCl2-Kryptofix (1.5 mol%)
Pd(OAc)2 (2 mol%)
[HEmim][BF4]
[BMIM][PF6]
DMF
57 [10b]
91 [13b]
89 [13c]
4
[BMIM][X]-Pd(OAc)2 (6 mol%)
CNT@Fe3O4@SiO2-Pd (1.5 mol%)
Pd-Salen@MWCNTs
c5
d6
24/130
5/130
DMF
85 [13d]
a Isolated yield. b, d 1mmol TBAB was used as additive. c 0.5 mmol TBAB was used as additive.

ACCEPTED MANUSCRIPT
A novel bis(imidazolium) chlorides as ligand precursor synthesized
Pd-catalyzed Mizoroki-Heck cross-coupling reactions was successfully performed
Performing the reaction with aryl chlorides and bromides
Moderate to excellent yields
Excellent regioselectivity for aryl bromides