Polystyrene-resin supported N-heterocyclic carbene-Pd(II) complex based on plant-derived theophylline: A reusable and effective catalyst for the Suzuki-Miyaura cross-coupling reaction of arenediazonium tetrafluoroborate salts with arylboronic acids

Article abstract of DOI:10.1016/j.jorganchem.2016.08.017

Polystyrene-supported NHC-Pd(II) complex based on theophylline as a sustainable NHC precursor was employed in the Suzuki-Miyaura cross-coupling reaction of substituted arenediazonium tetrafluoroborate salts with a variety of arylboronic acids to afford functionalized biaryl derivatives in good to excellent yields without using base or additive as promoters. The catalyst was easily recovered by ?ltration and reused for six successive cycles.

Full text of DOI:10.1016/j.jorganchem.2016.08.017

Accepted Manuscript
Polystyrene-resin supported N-heterocyclic carbene-Pd(II) complex based on plant-
derived theophylline: A reusable and effective catalyst for the Suzuki-Miyaura cross-
coupling reaction of arenediazonium tetrafluoroborate salts with arylboronic acids
Elmira Mohammadi, Barahman Movassagh
PII:
S0022-328X(16)30351-5
10.1016/j.jorganchem.2016.08.017
JOM 19596
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 14 June 2016
Revised Date: 15 August 2016
Accepted Date: 16 August 2016
Please cite this article as: E. Mohammadi, B. Movassagh, Polystyrene-resin supported N-heterocyclic
carbene-Pd(II) complex based on plant-derived theophylline: A reusable and effective catalyst for the
Suzuki-Miyaura cross-coupling reaction of arenediazonium tetrafluoroborate salts with arylboronic acids,
Journal of Organometallic Chemistry (2016), doi: 10.1016/j.jorganchem.2016.08.017.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract:
Suzuki-Miyaura cross-coupling reaction between aromatic diazonium tetrafluoroborate salts and
arylboronic acids was carried out in the presence of polystyrene-supported palladium(II)-NHC. This
methodology provides an efficient and mild approach towards the synthesis of biaryl derivatives.
O
N
N
N
I
N
O
N
N
N
O
O
N
N
O
O
O
N
N
N
N
PS
N
P
d
O
N
I
N
N
N
N
N
O
O
N
N
O
N
N
O

ACCEPTED MANUSCRIPT
Polystyrene-resin supported N-heterocyclic carbene-Pd(II) complex based on plant-derived
theophylline: A reusable and effective catalyst for the Suzuki-Miyaura cross-coupling
reaction of arenediazonium tetrafluoroborate salts with arylboronic acids
Elmira Mohammadi, Barahman Movassagh*
Department of Chemistry, K. N. Toosi University of Technology, P.O. Box 16315-1618, Tehran,
Iran; Tel: +98-21-23064323; E-mail: bmovass1178@yahoo.com
Abstract
Polystyrene-supported NHC-Pd(II) complex based on theophylline as a sustainable NHC
precursor was employed in the Suzuki-Miyaura cross-coupling reaction of substituted
arenediazonium tetrafluoroborate salts with a variety of arylboronic acids to afford
functionalized biaryl derivatives in good to excellent yields without using base or additive as
promoters. The catalyst was easily recovered by filtration and reused for six successive cycles.
Keywords: Arenediazonium tetrafluoroborate salts; Suzuki-Miyaura reaction; N-heterocyclic Carbene;
C‒C Coupling; Polystyrene; Biaryl derivatives.

ACCEPTED MANUSCRIPT
1. Introduction
Nowadays, the construction of carbon-carbon and carbon-heteroatom bonds based on palladium-
catalyzed cross-coupling reactions have proven to be a powerful synthetic tool in modern organic
synthesis [1]. Among, the various Pd-mediated strategies developed to date, the Suzuki-Miyaura
reaction has been considered as a vital organic transformation, since the resultant biphenyl
derivatives play a pivotal role in a wide range of natural products, pharmaceuticals, and materials
science [2-5]. The traditional Suzuki-Miyaura reaction include, the cross-coupling reaction of
alkyl- as well as arylboronic acids with aryl halides. Also, other organometallic reagents such as
aryl zinc (Negishi coupling) [6], aryl magnesium (Kumada coupling) [7], and aryl silanes
(Hiyama coupling) [8] have been used as coupling partners with aryl halides for the construction
of biaryls. However, for all of the above-mentioned coupling reactions, costly aryl halides have
been commonly used as an electrophilic component. In addition to economic aspects, the
methodologies that are based on aromatic halides require a base, an additive, and an elevated
temperature which limits the scope of these protocols. Therefore, during the past few decades,
the Suzuki-Miyaura reaction has witnessed dramatic developments in the investigation of
suitable electrophilic agents, instead of expensive aryl halides. In this context, many alternative
electrophilic species such as aryl triflates [9], aryl mesylates [10], and O-aryl carbamates [11]
have been developed. Besides the difficulties in the preparation of these species, most of the
methodologies using these alternative coupling components suffer from harsh reaction
conditions, long reaction times, and low tolerance of functional groups. Thus, in recent years to
enlarge the scope of the Suzuki-Miyaura reaction, generating suitable electrophilic coupling
partner has been receiving an increasing interest. Among many electrophilic coupling
components, aromatic diazonium salts (ADS) are found to be an attractive choice due to their
high reactivity and easy preparation methods. Also, arenediazonium salts are known as valuable
and versatile reagents in organic syntheses and utilized in many organic transformations [12].
ADS can be considered as superelectrophiles since they are armed with diazonium function (N2)
as nucleofuge, which allows the cross-coupling reactions to proceed efficiently under a simple
and mild experimental procedure. In comparison to the typical Suzuki-Miyaura reaction,
employing arenediazonium tetrafluoroborate salts as a coupling component provides a base-free,
energy- and cost-saving protocol. Although palladium-catalyzed cross-coupling reaction of
+
̶
arenediazonium tetrafluoroborate salts (ArN2 BF4 ) and arylboronic acids have been performed

ACCEPTED MANUSCRIPT
by diverse homogeneous [13] as well as heterogeneous catalysts [14], there is a resurgent interest
in the development of efficient methods for this transformation. From the growing list of
organometallic complexes, N-heterocyclic carbenes (NHCs) and their transition metal complexes
have been widely used as catalysts in organic reactions due to their potential catalytic activity,
air- and thermal stability, and moisture resistant features [15]. NHCs as spectator ligands with
high σ-donor and negligible π-accepting ability bear similarities to the phosphine ligands, that
were initially recognized as mimics for this ubiquitous class of ligands in transition-metal
coordination chemistry [16]. The major applications of the metal-NHC complexes involve
coordination polymers [17], photoactive materials [18], olefin metathesis [19], C-H activation
protocols [20], C-C [21] and C-heteroatom bond forming reactions [22]. Recently, heterogeneous
organometallic catalysts have gained much importance in cross-coupling reactions, since
homogeneous catalysts have some disadvantages in terms of the recycling of the catalysts,
contamination of metal residue in the final product, and destruction of catalysts during the course
of the reaction. In order to overcome these drawbacks, many organic and inorganic solid
supports have been designed and developed for encapsulation or immobilization of the
catalytically active organometallic complexes [23]. In view of many efficient solid supports
containing NHC-metal complexes, polymers are of great interest owing to the fact that they are
inexpensive, thermally stable, chemically inert, and non-toxic. Very recently, we reported a
reusable and efficient polystyrene-supported NHC-Pd(II) complex derived from theophylline 3
as the catalyst for the Heck-Matsuda cross-coupling reaction of activated and non-activated
arenediazonium tetrafluoroborate salts with olefins that gave arylated olefins in good to excellent
yields [24]. This heterogeneous NHC-Pd(II) catalyst has been prepared from naturally occurring
xanthine derivative theophylline, which can be considered as sustainable plant-derived NHC
precursor. As part of our ongoing research on heterogeneous organometallic complexes [25],
herein we present the use of reusable PS-NHC-Pd(II) complex, catalyzing the coupling of
functionalized aromatic diazonium tetrafluoroborate salts with diverse arylboronic acids under
additive- and base-free conditions at room temperature which exhibits the efficiency of our
polystyrene-supported NHC catalyst.

ACCEPTED MANUSCRIPT
2. Results and discussion
The polystyrene-supported NHC-Pd(II) (Fig. 1) complex was synthesized according to our
previously reported procedure [24]. The palladium content of the PS-NHC-Pd(II) was
determined by inductively coupled plasma (ICP) and was found to be 3.31 wt% (0.31
Figure 1. Heterogeneous PS-NHC-Pd(II) catalyst.
mmol/g) in the catalyst. As a starting point in the investigation of the best operating experimental
conditions, the Suzuki-Miyaura coupling reaction between 4-bromobenzenediazonium
tetrafluoroborate and phenylboronic acid was selected as the representative substrate. The data
are listed in Table 1. Since the performance of the Suzuki-Miyaura cross-coupling reaction of
arenediazonium tetrafluoroborate salts and arylboronic acids is dependent on a variety of
parameters, such as solvent, temperature, molar ratios of the substrates and the amount of the
catalyst, all of these factors were studied during the optimization of the reaction. From the results
given in Table 1, it can be concluded that among the different solvents tested at 40 ºC,
unsatisfactory results were obtained with aprotic solvents (Table 1, entries 1-4). Comparatively,
in the case of the protic solvents, methanol (MeOH) was found to be the most effective reaction
media, improving the yield of the desired product to 98% (Table 1, entry 5). On the other hand,
when water was employed as the reaction solvent, no coupling adduct was observed even after
24 h (Table 1, entry 7). Furthermore, the yield of the model reaction was dramatically decreased
when a 1:1 mixture of MeOH:H2O was used (Table 1, entry 8). Reducing the reaction
temperature from 40 ºC to 25 ºC had no effect on the product yield (Table 1, entry 9).
Additionally, when the temperature was raised to 50 ºC, no remarkable improvement was
observed in the reaction conversion or time (Table 1, entry 10). In searching for the optimal
molar ratios of the diazonium salt and arylboronic acid, we screened various ratios, among which

ACCEPTED MANUSCRIPT
1:1.1 ratio of the 1 : 2 was found to give the best result (Table 1, entry 9). When 1:1 ratio of
coupling components was used the yield of the reaction product dropped to 52% (Table 1, entry
12), proving the fact that an excess amount of arylboronic acid is needed to initiate the catalytic
cycle by reduction of Pd(II) to active Pd(0) species. To investigate the effect of the catalyst
loading on the yield of the cross-coupling reaction, 0.5, 1.0, and 1.5 mol% of the catalyst were
studied. When the reaction was carried out in the presence of the 0.5 mol% of the PS-NHC-
Pd(II) catalyst, the yield of the desired product was notably diminished to 78% (Table 1, entry
14). An increase in the catalyst concentration to 1.5 mol% did not have any significant effect on
the reaction rate (Table 1, entry 15). In situ generation of the 4-bromobenzenediazonium
tetrafluoroborate using 4-bromoaniline, boron trifluoride diethyl etherate (BF3.OEt2), and
tBuONO in dry THF was also studied; it was found that due to the low solubility of 4-
bromobenznediazonium tetrafluoroborate salt in THF, only 21% of the coupling adduct was
formed at 25 ºC after 24 h (Table 1, entry 16). Finally, the optimal reaction conditions of 1:1.1
ratio of arenediazonium tetrafluoroborate salts to arylboronic acids and 1 mol% PS-NHC-Pd(II)
in MeOH at room temperature were chosen for further investigations.
Table 1. Optimization of the reaction of 4-bromobenezenediazonium tetrafluoroborate and phenylboronic
acid as model substrates.a
Temp.
(ºC)
40
Time Molar ratios of substrates
Cat.
Entry
Solvent
Yieldb (%)
(h)
24
18
24
24
3
(1 : 2)
1:1.1
1:1.1
1:1.1
1:1.1
1:1.1
1:1.1
1:1.1
1:1.1
1:1.1
(mol% of Pd)
1
2
3
4
5
6
7
8
9
DMSO
THF
1
1
1
1
1
1
1
1
1
40
45
40
Dioxane
CH3CN
MeOH
40
trace
trace
98
40
40
EtOH
40
5
79
H2O
40
24
24
3
N.R.
36
MeOH:H2O (1:1)
MeOH
40
25
98

ACCEPTED MANUSCRIPT
10
11
12
13
14
15
16c
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
THF
50
25
25
25
25
25
25
3
3
1:1.1
1:1.3
1:1
1
1
97
98
52
88
78
96
21
3
1
3
1.3:1
1:1.1
1:1.1
1:1.1
1
3
0.5
1.5
1
3
24
a Reaction conditions: 4-bromobeneznediazonium tetrafluoroborate salt, phenylboronic acid, and PS-NHC-Pd(II)
catalyst in solvent (1 mL).
b Isolated yields.
c
4-Bromobeneznediazonium tetrafluoroborate salt (1) was generated in situ using 4-bromoaniline, BF3.OEt2 and
tBuONO.
After successful development of the optimal reaction conditions, we further proceeded to explore
the scope of the Suzuki-Miyaura cross-coupling reaction of various aromatic diazonium
tetrafluoroborate salts with arylboronic acids (Table 2). As shown in Table 2, the coupling
reaction tolerated electron rich as well as electron withdrawing functionalities on the aromatic
ring of diazonium tetrafluoroborate salts, to afford coupling products in good to excellent yields
(Table 2, entries 1-28). However, diazonium substrates bearing electron withdrawing groups,
such as p-NO2, m-NO2, o-NO2, and m-CN gave high yields of the corresponding adducts in
shorter reaction times (Table 2, entries 15-23). Additionally, compared with the corresponding
para-substituted arenediazonium tetrafluoroborate salts, the yields of the ortho-substituted
derivatives dropped slightly due to the steric demands (Table 2, entries 7 and 10, 11 and 14, 15
and 22). Furthermore, chemoselectivity of the methodology was screened by employing halide-
substituted diazonium salts, and, in all cases, no typical Suzuki-Miyaura cross-coupling reaction
between halide and arylboronic acid was observed (Table 2, entries 24-28). Also, a range of
substituted arylboronic acids was examined. As can be seen from Table 2, para- and meta-
substituted arylboronic acids successfully coupled with arenediazonium tetrafluoroborate salts,
while sterically hindered ortho-substituted arylboronic acids, such as ortho-methyl and ortho-
methoxyphenylboronic acid exhibited lower yields of the desired products (Table 2, entries 3 and
5). Furthermore, when 1-naphthylboronic acid was employed in the cross-coupling reaction, the
yields of the products were decreased, which can be attributed to the steric effect of the peri-
hydrogen (Table 2, entries 6 and 20).

ACCEPTED MANUSCRIPT
The reusability of heterogeneous catalysts is very important, especially for commercial
applications. Thus, the recyclability of the catalyst was examined by carrying out repeated runs
on the same batch of 1 mol% PS-NHC-Pd(II) catalyst used in the cross-coupling reaction of 4-
bromobenzenediazonium tetrafluoroborate salt (1 mmol) and phenylboronic acid (1.1 mmol)
under the reaction conditions. After the completion of each cycle, the catalyst was easily
recovered by simple filtration and washed with H2O and MeOH. Then, it was dried in an
Table 2. PS-NHC-Pd(II)-catalyzed Suzuki-Miyaura cross-coupling reaction of functionalized
arenediaznonium salts with diverse arylboronic acids.a
Entry
1
Ar
Ar'
Time (h)
Yield (%)b
86
C6H5
C6H5
3
3
2
C6H5
4-MeC6H4
2-MeC6H4
4-MeOC6H4
2-MeOC6H4
1-naphthyl
C6H5
90
3
C6H5
3
81
4
C6H5
3.33
3.5
4.5
3
79
5
C6H5
66
6
C6H5
83
7
4-MeC6H4
4-MeC6H4
C6H5
86
8
4-MeOC6H4
3-MeC6H4
C6H5
3
81
9
3
58
10
11
12
13
14
15
16
17
18
19
2-MeC6H4
4-MeOC6H4
4-MeOC6H4
4-MeOC6H4
2-MeOC6H4
4-NO2C6H4
4-NO2C6H4
4-NO2C6H4
4-NO2C6H4
4-NO2C6H4
3.5
3
78
C6H5
86
4-MeOC6H4
4-MeC6H4
C6H5
3
84
3
81
3.66
2
84
C6H5
92
4-MeC6H4
3-MeC6H4
4-MeOC6H4
3-MeOC6H4
2
96
2
94
1.66
1.66
92
89

ACCEPTED MANUSCRIPT
20
21
22
23
24
25
26
27
4-NO2C6H4
3-NO2C6H4
2-NO2C6H4
3-CNC6H4
4-BrC6H4
4-IC6H4
1-naphthyl
C6H5
3
2
72
91
87
93
98
98
84
81
C6H5
2
C6H5
1.66
3
C6H5
C6H5
3
4-IC6H4
4-MeC6H4
4-MeOC6H4
3
4-ClC6H4
3
28
2-ClC6H4
C6H5
3
63
a
Reaction conditions: arenediazonium tetrafluoroborate salt (0.5 mmol), arylboronic acid (0.55 mmol), and PS-
NHC-Pd(II) catalyst (1 mol%) in MeOH (1 mL).
b Isolated yields.
oven at 100 ºC for 2 h before being used for the next round of the reaction. The catalyst activity
was not considerably diminished even after six reaction cycles (Fig. 2). Furthermore, to
determine whether the catalyst is truly functioning in a heterogeneous manner, a hot filtration
test was performed in the cross-coupling reaction of 4-bromobenzenediazonium tetrafluoroborate
and phenylboronic acid under the reaction conditions. During the catalytic reaction, the solid
catalyst was removed from the reaction mixture by filtration after 1.5 h and the determined
conversion was 53%. The residual solution was, then, allowed to react for further 1.5 h and the
obtained conversion was the same (53%). Also, the amount of the Pd species dissolved into
solution caused by leaching of the catalyst was determined using ICP after evaporation of the
solution to dryness. The ICP result showed that 0.09% of the total amount of the original Pd
species is lost into solution during the course of the reaction. This results suggested that minimal
leaching of palladium takes place during the reaction and the catalyst is purely heterogeneous in
nature.
Further evidence for the attachment of NHC-Pd(II) onto the polymeric support is confirmed by
X-ray photoelectron spectroscopy (XPS) analysis of the recovered PS-NHC-Pd(II) catalyst (Fig.
3a). As depicted in Fig. 3b, the binding energies around 337.58 and 342.98 eV with good
resolution and intensity are attributed to Pd(II) 3d3/2 and 3d5/2 electrons, respectively, confirming
the presence of only Pd(II) in the recovered catalyst [26].

ACCEPTED MANUSCRIPT
Figure 2. Recycling activity of the PS-NHC-Pd(II) catalyst in the reaction of 4-
bromobenzenediazonium tetrafluoroborate with phenylboronic acid.
(a)
(b)
Figure 3. Full range XPS spectrum (a) of the recovered PS-NHC-Pd(II) catalyst, and Pd 3d (b)
spectra of the fresh and recovered catalyst.
3. Conclusion
In conclusion, we have shown that the Suzuki-Miyaura cross-coupling reaction of
arenediazonium tetrafluoroborate salts and arylboronic acids in the presence of polymer-

ACCEPTED MANUSCRIPT
supported NHC-Pd(II) complex represents an elegant route to functionalized biaryls. Diverse
aromatic diazonium salts were cross-coupled efficiently with arylboronic acids. The procedure is
simple, general, economical, additive- and base-free, affording the desired products in good to
excellent yields. Furthermore, this heterogeneous plant-derived catalyst can be simply recovered
and reused up to six cycles.
4. Experimental
All materials were commercial grade and purchased from Aldrich, Merck, and Fluka.
Chloromethylated polystyrene resin cross-linked with 2% DVB (200-400 mesh, 2.8-3.2 mmol/g
of Cl) was a product of Acros chemicals. Benzenediazonium tetrafluoroborate salt and its
derivatives were all known and prepared according to the literature method [27]. The PS-NHC-
1
Pd(II) catalyst was synthesized according to our previously reported procedure. H (300 MHz)
and 13C NMR (75 MHz) spectra of the final Suzuki-Miyaura products were recorded on a Bruker
AQS-300 Avance spectrometer. The NMR spectra of the compounds in Table 2 are given in
electronic supporting information (ESI). The Pd content of the complex was determined using
ICP (Varian vista-mpx), and the XPS data were recorded using an 8025-BesTec twin anode
XR3E2 X-ray source system.
4.1. General procedure for the Suzuki-Miyaura cross-coupling reaction
Under aerial atmosphere, a test tube was charged with arenediazonium tetrafluoroborate salt (0.5
mmol), PS-NHC-Pd(II) complex (17 mg, 1 mol%), and MeOH (1 mL). After the addition of
arylboronic acid (0.55 mmol), the mixture was stirred at room temperature for an appropriate
time. The progress of the reaction was monitored by TLC. After the completion of the reaction,
the mixture was filtered to recover the catalyst and the filtrate was concentrated under vacuuo.
Furthermore, the reaction mixture was extracted with CH2Cl2 (2 × 5 mL) and the combined
organic layer was washed with water (2 × 5 mL). The organic layer was dried over Na2SO4 and
the solvent evaporated under reduced pressure. The residue was purified by a preparative thin
layer chromatography plate, using 10% EtOAc in n-hexane as eluent.

ACCEPTED MANUSCRIPT
Acknowledgements
Financial support from K. N. Toosi University of Technology Research Council is
gratefully acknowledged. The authors are grateful to Dr. Sogand Noroozizadeh for revising
the English language of the manuscript.
References
[1]
(a) A. Molnar, Palladium-Catalyzed Coupling Reactions. Practical Aspects and Futur
Developments, Wiley-VCH, Weinheim, 2013;
(b) C.C.C.J. Seechurn, M.O. Kitching, T.J. Colacot, V. Snieckus, Angew. Chem. Int. Ed. 51
(2012) 5062-5085;
(c) V.P. Mehta, E.V. Van der Eycken, Chem. Soc. Rev. 40 (2011) 4925-4936;
(d) K.C Nicolaou, P.G. Bulger, D. Sarlah, Angew. Chem. Int. Ed. 44 (2005) 4442-4489.
J. Hassan, M. Sévignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev. 102 (2002) 1359-1470.
S. Kohta, K. Lahiri, D. Kashinath, Tetrahedron 58 (2002) 9633-9695.
A. Suzuki, Angew. Chem. Int. Ed. 50 (2011) 6722-6737.
J.D. Sellars, P.G. Steel, Chem. Soc. Rev. 40 (2011) 5170-5180.
(a) M.G. Organ, S. Avola, I. Dubovyk, N. Hadei, E.A.B. Kantchev, C.J. O'Brien, C. Valente,
Chem. Eur. J. 12 (2006) 4749-4755;
[2]
[3]
[4]
[5]
[6]
(b) Y. Yang, N.J. Oldenhuis, S.L. Buchwald, Angew. Chem. Int. Ed. 52 (2013) 615-619.
(a) R. Martin, S.L. Buchwald, J. Am. Chem. Soc. 129 (2007) 3844-3845;
(b) V. Bonnet, F. Mongin, F. Trécourt, G. Quéguiner, P. Knochel, Tetrahedron 58 (2002) 4429-
4438.
(a) S.E. Denmark, C.S. Regens, Acc. Chem. Res. 41 (2008) 1486-1499;
(b) O.Y. Yuen, C.M. So, H.W. Man, F.Y. Kwong, Chem. Eur. J. 22 (2016) 6471-6476;
(c) B. Movassagh, F.S. Parvis, M. Navidi, Appl. Organomet. Chem. 29 (2015) 40-44.
(a) G. Espino, A. Kurbangalieva, J.M. Brown, Chem. Commun. (2007) 1742-1744;
(b) A.F. Littke, C. Dai, G.C. Fu, J. Am. Chem. Soc. 122 (2000) 4020-4028;
(c) K.-Q. Zhao, Y. Gao, W.-H. Yu, P. Hu, B.-Q. Wang, B. Heinrich, B. Donnio, Eur. J. Org.
Chem. doi: 10.1002/ejoc.201600270.
[7]
[8]
[9]
[10]
[11]
(a) K.H. Chung, C.M. So, S.M. Wong, C.H. Luk, Z. Zhou, C.P. Lau, F.Y. Kwong, Chem.
Commun. 48 (2012) 1967-1969;
(b) B. Bhayana, B.P. Fors, S.L. Buchwald, Org. Lett. 11 (2009) 3954-3957.
(a) K.W. Quasdorf, A. Antoft-Finch, P. Liu, A.L. Silberstein, A. Komaromi, T. Blackburn, S.D.
Ramgrent, K.N. Houk, V. Snieckus, N.K. Garg, J. Am. Chem. Soc. 133 (2011) 6352-6363;
(b) K.W. Quasdorf, M. Riener, K.V. Petrova, N.K. Garg, J. Am. Chem. Soc. 131 (2009) 17748-
17749.
[12]
[13]
Zollinger, H., Diazo Chemistry, Weinheim, New York, Basel, Cambridge, Tokyo, 1994.
(a) S. Sengupta, S. Bhattacharyya, J. Org. Chem. 62 (1997) 3405-3406;
(b) M.B. Andrus, C. Song, Org. Lett. 3 (2001) 3761-3764;
(c) K. Selvakumar, A. Zapf, A. Spannenberg, M. Beller, Chem. Eur. J. 8 (2002) 3901-3906;
(d) M. Dai, B. Liang, C. Wang, J. Chen, Z. Yang, Org. Lett. 6 (2004) 221-224;
(e) D. Mingji, B. Liang, C. Wang, Z. You, J. Xiang, G. Dong, J. Chen, Z. Yanga, Adv. Synth.
Catal. 346 (2004) 1669-1673;
(f) B. Schmidt, F. Hölter, Org. Biomol. Chem. 9 (2011) 4914-4920.

ACCEPTED MANUSCRIPT
[14]
(a) Y. Qin, W. Wei, M. Luo, Synlett 2007 (2007) 2410-2414;
(b) F.X. Felpin, E. Fouquet, Adv. Synth. Catal. 350 (2008) 863-868;
(c) F.X. Felpin, E. Fouquet, C. Zakri, Adv. Synth. Catal. 351 (2009) 649-655;
(d) Y. Zong, J. Hu, P. Sun, X. Jiang, Synlett 23 (2012) 2393-2396;
(e) K.E. Balsane, S.S. Shendage, J.M. Nagarkar, J. Chem. Sci. 127 (2015) 425-431.
M.N. Hopkinson, C. Richter, M. Schedler, M.; F. Glorius, Nature 510 (2014) 485-496.
R.H. Crabtree, J. Organomet. Chem. 690 (2005) 5451–5457.
A.J. Boydston, K.A. Williams, C.W. Bielawski, J. Am. Chem. Soc. 127 (2005) 12496–12497.
R. Visbal, M.C. Gimeno, Chem. Soc. Rev. 43 (2014) 3551–3574.
(a) C. Samojłowicz, M. Bieniek, K. Grela, Chem. Rev. 109 (2009) 3708–3742;
(b) G.C. Vougioukalakis, R.H. Grubbs, Chem. Rev. 110 (2010) 1746–1787.
(a) E.D. Coy, L.E. Cuca, M. Sefkow, Synth. Commun. 41 (2010) 41-51;
(b) D. Munz, D. Meyer, T. Strassner, Organometallics 32 (2013) 3469-3480.
(a) C.I. Ezugwu, B. Mousavi, M.A. Asrafa, A. Mehta, H. Vardhan, F. Verpoort, Catal. Sci.
Technol. 6 (2016) 2050-2054;
[15]
[16]
[17]
[18]
[19]
[20]
[21]
(b) L. Seva, W.-S. Hwang, S. Sabiah, J. Mol. Catal. A: Chem. 418-419 (2016) 125-131;
(c) S. Xu, K. Song, T. Li, B. Tan, J. Mater. Chem. A 3 (2015) 1272-1278.
(a) C. Valente, M. Pompeo, M. Sayah, M.G. Organ, Org. Process Res. Dev. 18 (2014) 180-190;
(b) G. Bastug, S.P. Nolan, J. Org. Chem. 78 (2013) 9303-9308.
(a) D.V. Jawale, E. Gravel, C. Boudet, N. Shah, V. Geertsen, H. Li, I.N.N. Namboothiri, E. Doris,
Catal. Sci. Technol. 5 (2015) 2388-2392;
[22]
[23]
(b) N. Oger, E. Le Grognec, F.-X. Felpin, Chem. Cat. Chem. 7 (2015) 2085-2094;
(c) Y. Ukisu, Reac. Kinet. Mech. Cat. 114 (2015) 385-394;
(d) R.N. d’Alnoncourt, M. Friedrich, E. Kunkes, D. Rosenthal, F. Girgsdies, B. Zhang, L. Shao,
M. Schuster, M. Behrens, R. Schlögl, J. Catal. 317 (2014) 220-228;
(e) Z. Chen, P. Zou, R. Zhang, L. Dai, Y. Wang, Catal. Lett. 145 (2015) 2029-2036;
(f) O.B. Ayodele, H.F. Abbas, W.M.A.W. Daud, Energy Fuels 28 (2014) 5872-5881;
(g) A. Kumbhar, R. Salunkhe, Curr. Org. Chem. 19 (2015) 2075-2121.
E. Mohammadi, B. Movassagh, J. Mol. Catal. A: Chem. 418-419 (2016) 158-167.
(a) B. Movassagh, A. Takallou, A. Mobaraki, J. Mol. Catal. A: Chem. 401 (2015) 55-65;
(b) B. Movassagh, N. Rezaei, Tetrahedron 70 (2014) 8885-8892;
[24]
[25]
(c) B. Movassagh, N. Rezaei, New J. Chem. 39 (2015) 7988-7997;
(d) M. Navidi, B. Movassagh, S. Rayati, Appl. Catal. A: General 452 (2013) 24-28;
(e) M. Navidi, N. Rezaei, B. Movassagh, J. Organomet. Chem. 743 (2013) 63-69.
V.N. Mikhaylov, V.N. Sorokoumov, K.A. Korvinson, A.S. Novikov, I.A. Balova,
Organometallics 35 (2016) 1684-1697.
[26]
[27]
(a) M. Bu, T.F. Niu, C. Cai, Catal. Sci. Technol. 5 (2015) 830-834;
(b) G. Danoun, B. Bayarmagnai, M.F. Grünberg, L.J. Goo
7972-7975;
βen, Angew. Chem. Int. Ed. 52 (2013)
(c) M.P. Doyle, W.J. Bryker, J. Org. Chem. 44 (1979) 1572-1574.

ACCEPTED MANUSCRIPT
Highlights
•
•
•
•
Polystyrene-supported NHC-Pd(II) were successfully used as heterogeneous catalyst.
Arenediazonium salts were cross-coupled with arylboronic acids.
Diverse biaryl derivatives obtained in 58-98% yields.
The catalyst was successfully reused for six consecutive runs.