Suzuki–Miyaura coupling reaction in water in the presence of robust palladium immobilized on modified magnetic Fe3O4 nanoparticles as a recoverable catalyst

Article abstract of DOI:10.1002/aoc.3993

Aryl halides and especially inactive aryl chlorides were coupled to benzenoid aromatic rings in a Suzuki–Miyaura coupling reaction in the absence of organic solvents and toxic phosphine ligands. The reaction was catalysed by a recoverable magnetic nanocatalyst, Pd@Fe₃O₄, in aqueous media. This method is green, and the catalyst is easily removed from the reaction media using an external magnetic field and can be re-used at least 10 times without any considerable loss in its activity. The catalyst was characterized using scanning and transmission electron microscopies, thermogravimetric analysis, inductively coupled plasma spectroscopy, Fourier transform infrared spectroscopy, CHN analysis, X-ray diffraction and vibrating sample magnetometry.

Full text of DOI:10.1002/aoc.3993

Received: 14 March 2017
DOI: 10.1002/aoc.3993
Revised: 27 June 2017
Accepted: 27 June 2017
F U L L P A P E R
Suzuki–Miyaura coupling reaction in water in the presence
of robust palladium immobilized on modified magnetic
Fe3O4 nanoparticles as a recoverable catalyst
Arefeh Dadras1 | M. Reza Naimi‐Jamal1
| Firouz Matloubi Moghaddam2
|
Seyed Ebrahim Ayati2
1 Department of Chemistry, Research
Aryl halides and especially inactive aryl chlorides were coupled to benzenoid
aromatic rings in a Suzuki–Miyaura coupling reaction in the absence of organic
solvents and toxic phosphine ligands. The reaction was catalysed by a recover-
able magnetic nanocatalyst, Pd@Fe3O4, in aqueous media. This method is
green, and the catalyst is easily removed from the reaction media using an
external magnetic field and can be re‐used at least 10 times without any consid-
erable loss in its activity. The catalyst was characterized using scanning and
transmission electron microscopies, thermogravimetric analysis, inductively
coupled plasma spectroscopy, Fourier transform infrared spectroscopy, CHN
analysis, X‐ray diffraction and vibrating sample magnetometry.
Laboratory of Green Organic Synthesis
and Polymers, Iran University of Science
and Technology, PO Box 16846‐11314,
Tehran, Iran
2 Department of Chemistry, Laboratory of
Organic Synthesis and Natural Products,
Sharif University of Technology, PO Box
11155‐9516, Tehran, Iran
Correspondence
M. Reza Naimi‐Jamal, Department of
Chemistry, Research Laboratory of Green
Organic Synthesis and Polymers, Iran
University of Science and Technology, PO
Box 16846‐11314, Tehran, Iran.
Email: naimi@iust.ac.ir
KEYWORDS
green chemistry, magnetic nanoparticle, nanomagnetic catalyst, palladium, Suzuki–Miyaura coupling
reaction, water
Funding information
Iran University of Science and Technology
1 | INTRODUCTION
high yields and easy work‐up.[7,8] Because of nanoparticle
size, they have a high ratio of surface area to volume,
Catalysts have many advantages in organic synthesis and
are divided into two general categories, heterogeneous
and homogeneous. Both have their own advantages and
disadvantages. For example, homogeneous catalysts are
more selective and because of being in the same phase
as reactants, they may result in higher reaction rate and
higher yields, but they are hard to separate from reaction
media, and therefore they may contaminate the final
product, which can be sometimes very harmful,
especially in drug synthesis.[1,2] Metals supported on
magnetic nanoparticles create a new approach in the
world of catalysts.[3,4] By the development of such
catalysts, it became possible to bring the advantages of
both kinds of catalysts (homogeneous and heteroge-
neous) together in a single magnetic nanocatalyst.[5,6]
This means one can profit from sustainability, along with
similar to a homogeneous catalyst. This property
increases the interaction between the reaction compo-
nents and so causes a marked increase in reaction rate
and yield.[9–11] These heterogeneous catalysts remain
insoluble in reaction media and, due to their magnetic
characteristic, they can be easily removed using an
external magnetic field.[12,13] Therefore, there is no
concern about separation of such catalysts and pollution
of products by toxic metals. Another important aspect is
their robust structure, which results in reusability for
several times that reduces environmental impact and
increases economic advantages.[14] Immobilization of
nanometals by strong sigma donor ligands not only min-
imizes metal leaching during a reaction, but also
minimizes the agglomeration of nanometals and pre-
serves the Fe3O4 magnetic core from over‐oxidation.[15,16]
Appl Organometal Chem. 2017;e3993.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 9
https://doi.org/10.1002/aoc.3993

2 of 9
DADRAS ET AL.
SCHEME 1 Synthesis of Fe3O4@SiO2@3‐
glycidoxypropyltrimethoxysilanetriazole@Pd.
As is known, palladium is a precious metal and is
by a co‐precipitation method,[35] functionalized using 3‐
glycidoxypropyltrimethoxysilane and then reacted with
phenylacetylene, sodium azide and copper chloride.[36]
To prepare the desired palladium catalyst, copper was
then removed via reaction with KCN, and palladium
was inserted by reaction with PdCl2 and KCl (Scheme 1).
useful in many organic transformations, especially in
Suzuki coupling. Biaryl compounds are of high impor-
tance and have many applications, so scientists are still
seeking for new ways to produce them in easier and
affordable ways.[17–21]
The Suzuki–Miyaura C–C cross‐coupling reaction
nowadays is of high importance in organic
synthesis.[22–28] This cross‐coupling reaction is generally
done with precious metal palladium in the presence of
hazardous, toxic, flammable and expensive ligands such
as hindered phosphines and carbenes in harmful organic
solvents like dimethylformamide, dioxane and toluene,
usually at high temperatures and with long reaction
times and low yields.[29–34] Herein, we introduce Fe3O4
magnetic nanoparticles, functionalized by triazole as an
efficient anchor for chelation of palladium. This catalyst
has been successfully used in Suzuki–Miyaura C–C
cross‐coupling reactions.
2 | RESULTS AND DISCUSSION
Fe3O4@SiO2@3‐glycidoxypropyltrimethoxysilane triazole
has been shown to be a strong ligand for chelating of cop-
per ions, resulting in a robust catalyst for click reactions,
without considerable leaching and with high reusability.
It was prepared as demonstrated in Scheme 1. Silica‐
coated Fe3O4 magnetic nanoparticles were synthesized
FIGURE 1 FT‐IR spectra of (a) Fe3O4, (b) Fe3O4@SiO2, (c)
Fe3O4@SiO2@3‐glycidoxypropyltrimethoxysilanetriazole and (d)
Fe3O4@SiO2@3‐glycidoxypropyltrimethoxysilanetriazole@Pd.

DADRAS ET AL.
3 of 9
FIGURE 2 TGA curve of the catalyst
of hydroxyl group band to lower wavelengths that is a
reasonable effect of the interaction between Pd and
hydroxyl groups of the catalyst.
According to the thermogravimetric analysis (TGA)
curve (Figure 2), decomposition of organic groups
starts at 250 °C and completes at 600 °C, which
corresponds to approximately 30% of the weight
(1.15 mmol g−1) of the catalyst and is a good indica-
tion for immobilization of triazole groups on the
magnetic core. The weight loss before 250 °C corre-
sponds to removal of adsorbed water. The stability of
the catalyst up to 250 °C indicates that the catalyst
has a good thermal stability.
FIGURE 3 SEM image of the catalyst
The scanning electron microscopy (SEM) image of the
catalyst (Figure 3) shows nanoparticles with spherical
morphology and an average size of around 50 nm. The
TEM image of the catalyst is shown in Figure 4, which
indicates a core–shell structure of the catalyst.
FIGURE 4 TEM image of the catalyst
The catalyst was characterized using Fourier trans-
form infrared (FT‐IR) spectroscopy (Figure 1). The peaks
at 650 and 1100 cm−1 correspond to Fe─O and Si─O
stretching vibrations of Fe3O4 and SiO2, respectively
(Figure 1a,b). The peaks at 2950 and 2930 cm−1 are
attributed to C─H stretching vibrations and indicate the
presence of alkylsilane groups on Fe3O4@SiO2 (Figure 1
c,d). As can be seen in Figure 1(d), there is a small shift
FIGURE 5 VSM curve of the catalyst

4 of 9
DADRAS ET AL.
TABLE 1 Optimizing of base, solvent and temperature in model reactiona
Entry
Base
Catalyst (mmol%)
Solvent
Temp. (°C)
Yield (%)b
1
—
1.2
H2O
80
NR
2
K2CO3
K2CO3
Na2CO3
Li2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
—
H2O
100
80
NR
98
3
1.2
1.2
1.2
0.6
1.2
0.6
1.2
0.6
0.6
H2O
4
H2O
80
30
5
H2O
80
25
6
Toluene
Toluene
H2O–t‐BuOHc
H2O–t‐BuOHc
H2O
100
100
80
Trace
Trace
7
7
8
9
80
18
10
11
100
80
40
H2O
40
aReaction conditions: p‐bromobenzene (0.5 mmol), phenylboronic acid (0.6 mmol), base (0.6 mmol), solvent (2 ml) and reaction time of 3 h.
bGC yield.
cRatio of H2O to t‐BuOH is 2:1.
TABLE 2 Suzuki–Miyaura C–C cross‐coupling reactions catalysed by palladium immobilized on modified magnetic Fe3O4 nanoparticlesa
Entry
Aryl halide (1)
Arylboronic acid (2)
Product (3)
Time (h)
Yield (%)b
1
3
98
2
3
4
5
2a
2a
2a
2a
3
3
3
3
98
97
92
94
6
7
2a
2a
3
3
96
96
8
2a
2a
3
4
97
72
9c
(Continues)

DADRAS ET AL.
5 of 9
TABLE 2 (Continued)
Entry
Aryl halide (1)
Arylboronic acid (2)
Product (3)
Time (h)
Yield (%)b
10
2a
3
93
11
12
1 g
2a
2a
3
3
95
90
13
1c
2a
2a
3c
3a
3
4
97
80
14c
15c
16c
2a
4
4
75
78
1 l
17
18
1 k
3
3
90
98
2b
2b
19
3
96
aReaction conditions: aryl halide (0.5 mmol), arylboronic acid (0.6 mmol), K2CO3 (0.6 mmol), catalyst (0.01 g), H2O (2 ml), 3 h at 80 °C.
bGC yield.
cReaction time = 4 h.
To investigate the amount of Pd loaded on the catalyst
support, inductively coupled plasma (ICP optical electron
spectrometry was used. The amount was estimated to be
about 13.2 wt% (1.2 mmol g−1). The ICP result proved that
there was a good Pd loading on the catalyst. No Cu
emission wavelength was detected. This means that all
Cu atoms were replaced by Pd ones.
According to CHN analysis, the content of carbon,
nitrogen and hydrogen in the catalyst was determined as
18.98, 3.02 and 2.30 wt%, respectively. This is in good
agreement with the structure of the catalyst, indicating
that a high level of alkylsilane groups (about 15.8 mmol
C per gram of catalyst) had been coated successfully on
the magnetic nanoparticles.
FIGURE 6 Reuse study of the catalyst in model reaction

6 of 9
DADRAS ET AL.
FIGURE 9 TEM image of recovered catalyst after reaction
FIGURE 7 FT‐IR spectra of the catalyst: (a) after reaction; (b)
before reaction
the most efficient base among those investigated
(Table 1, entry 3). Water, toluene and a mixture of water
and t‐BuOH were investigated, and it was found that
water was the best solvent. When the amount of the
catalyst based on palladium was increased from 0.60 to
1.20 mmol%, the yield increased from 40 to 98% at the
same time (compare entries 11 and 3).
After optimization of the reaction conditions, the
scope of the method was investigated with other aryl
halides and phenylboronic acid derivatives. The results
are summarized in Table 2. Using this catalyst, aryl
halides with both electron‐donating and electron‐with-
drawing groups are easily coupled with phenylboronic
acids (e.g. entries 3–6). Interestingly, generally
challenging inactive aryl chlorides were also reacted
with boronic acids to afford high yield of coupling
products (e.g. entries 14–16).
The magnetic property of the catalyst was investigated
at room temperature using vibrating sample magnetome-
try (VSM). According to Figure 5, the saturation magneti-
zation of the catalyst is about 37 emu g−1 with a magnetic
field within the range − 10 000 to 10 000 Oe. For a
magnetic catalyst, this magnetization value is enough to
allow it to be separated from reaction media by applying
an ordinary external magnetic field.
After careful characterization of the catalyst, its use-
fulness in Suzuki–Miyaura reactions was investigated.
For optimizing temperature, time, solvent and suitable
base for these coupling reactions, phenylboronic acid
and p‐bromobenzene were chosen as model reactants.
The results are summarized in Table 1. The reaction was
monitored using TLC, and the yields were determined
by GC. From Table 1, it is obvious that in the absence
of a base or catalyst, no reaction occurs (Table 1, entries
1 and 2). Inorganic strong bases like NaOH are
unsuitable, as they destroy the catalyst; therefore, alkali
metal carbonates as weak bases were investigated
(Table 1, entries 3–5). Potassium carbonate seems to be
In order to examine the reusability of the magnetic
heterogeneous palladium catalyst, it was collected
after each run by applying an external magnetic field,
FIGURE 10 X‐ray diffraction pattern of (a) the catalyst and (b)
FIGURE 8 SEM image of recovered catalyst after reaction
standard Fe3O4 sample

DADRAS ET AL.
7 of 9
TABLE 3 Comparison of various catalysts for Suzuki–Miyaura coupling reaction of chlorobenzene and phenylboronic acid
Time Temp. Yield
Entry Catalyst
Solvent
(h)
(°C)
(%)
Ref.
1
Fe3O4@SiO2@3‐glycidoxypropyltrimethoxysilanetriazole@Pd
H2O
5
80
75
Present
work
[37]
2
3
4
Pd(II)–NiFe2O4
EtOH–H2O 15
80
40
[38]
[39]
MNP‐supported di(2‐pyridyl)methanol–Pd complex
DMF
20
15
100
80
<20
34
Dichloridobis{(4‐diphenylphosphinylbenzenecarboxylic acid‐4‐[N‐(3‐
Dioxane
trimethoxysilypropyl)amide]}palladium(II)
[28]
[40]
[41]
[29]
[42]
5
6
7
8
9
Pd/UiO‐66 (MOF)
H2O–EtOH 20
H2O–EtOH 8
80
80
80
RT
80
70
45
87
64
74
Fe3O4/SiO2‐met‐Pd(OAc)2
Ethylenediamine‐functionalized graphene oxide‐immobilized Pd complex
Pd[tBuNH(S)NHP(O)(OiPr)2S]2Cl2 complex
Hollow Fe3O4‐NH2‐Pd
EtOH
DMF
20
14
H2O–EtOH 10
washed two times with methanol, dried and reused. As
shown in Figure 6, the catalyst can be used at least 10
times without any negligible reduction in its activity.
The structure of the catalyst was re‐investigated after
10 cycles using by FT‐IR spectroscopy, and no variation
was seen for the catalyst structure (Figure 7). The Pd
content was also determined by after 10 cycles using
atomic absorption spectroscopy, and showed no signifi-
cant loss of Pd (1.16 mmol g−1).
SEM (Figure 8) and TEM (Figure 9) images of the
catalyst after recovery give a good indication for the
stability of the catalyst after 10 cycles.
Figure 10 shows the powder X‐ray diffraction patterns
of the catalyst and neat Fe3O4 sample. According to the
diffraction peak positions and intensities, the modifica-
tion does not affect the crystalline structure of the Fe3O4
particles.
In order to confirm that the progress of the reaction is
due to the immobilized palladium (verifying the
heterogeneous nature of the catalyst) and not leached
homogeneous palladium in solution, a hot filtration test
was conducted. After 1 h progress of the coupling reaction
of iodobenzene with phenylboronic acid, the catalyst was
collected using an external magnetic field, and the
reaction was continued for the remaining time in
the absence of the catalyst. No further conversion was
observed in liquid phase, which is a good indication of
the heterogeneity of the catalyst and verifies that there is
no significant leaching.
A comparison between the efficacy of our reported
catalyst and some other palladium‐based catalysts for aryl
chloride coupling is presented in Table 3 for the
model reaction. It is apparent that our catalyst works well
in reasonably short reaction times and under mild
reaction conditions, in water as a green solvent.
3 | CONCLUSIONS
We have used palladium immobilized on Fe3O4
nanomagnetic core in C–C coupling reactions in the
absence of poisonous ligands in water as a green medium
in short reaction times with high yields and purity.
Different derivatives of biaryl compounds were produced
by reaction of phenylboronic acid derivatives and aryl
halides. The ability of this catalyst to couple inactive
aryl chlorides with phenylboronic acid is of high interest.
The catalyst also was easily removed from reaction media
using an external magnetic field, washed with methanol
and reused for 10 cycles without considerable reduction
in its reactivity. The stability of the catalyst to air,
moisture and heat is another benefit of this catalyst. Easy
and complete elimination of the catalyst from reaction
media is a good reason for using this catalyst in
pharmaceutical and drug synthesis.
4 | EXPERIMENTAL
4.1 | General
All chemicals and solvents were purchased from
commercially available sources such as Sigma‐Aldrich
and Merck and there was no need for any additional
purification. 1H NMR and 13C NMR spectra were
recorded with a Bruker (Avance DRX‐400) spectrometer
in CDCl3 as solvent at room temperature. Chemical shifts
were measured in ppm relative to tetramethylsilane as an
internal standard. An ABB Bomem MB‐100 FT‐IR
spectrophotometer was used for obtaining FT‐IR spectra
of samples. The morphology of the catalyst was
investigated using a Philips XL30 SEM instrument. TGA

8 of 9
DADRAS ET AL.
was conducted under a nitrogen atmosphere with a
TGA Q 50 thermogravimetric analyser. CHN analysis
was carried out with a LECO Truspec.
extracted, washed with methanol (3 × 20 ml) and dried
under reduced pressure.[36]
4.2.3 | Synthesis of Fe3O4@SiO2@3‐
glycidoxypropyltrimethoxysilane@triazole
4.2 | General procedure for catalyst
preparation
In order to exchange copper with palladium,
potassium cyanide (1.5 g) was dissolved in water–metha-
nol (1:1, 10 ml) and the solution was added to
Fe3O4@SiO2@triazole@Cu, which was synthesized in
the previous step and stirred for 5 h at room temperature.
Then, the catalyst was removed using an external
magnetic field, washed with methanol and dried over-
night at room temperature.
This catalyst was synthesized according to the procedure
reported in the literature (Scheme 1).[36]
4.2.1 | Synthesis of Fe3O4@SiO2
A solution of FeCl3 (66.58 mmol, 10.8 g) and FeCl2
(31.56 mmol, 4.0 g) was prepared in a three‐necked flask
in deionized water (50 ml). A solution of ammonium
hydroxide (28% v/v) was added dropwise to the solution
under an atmosphere of argon to adjust the pH to 10
and the solution was stirred for about 20 min at room
temperature. The prepared magnetic nanoparticles were
collected using an external magnetic field and washed
with deionized water (30 ml) and then three times with
ethanol (30 ml). The synthesized Fe3O4 nanoparticles
were dispersed in ethanol (80 ml) for 20 min using
ultrasonic irradiation (ultrasonic power: 100 W). These
magnetic nanoparticles were coated with silica through
the addition of 3 ml of tetraethyl orthosilicate (TEOS) to
the solution. While the solution was stirring, 3 ml of
ammonium hydroxide (28% v/v) was added to the mixture
during 15 min. The mixture was stirred for 12 h at 40 °C.
Finally, the silica‐coated magnetic nanoparticles
(Fe3O4@SiO2) were collected using an external magnet
and washed three times with ethanol (30 ml) and dried
in a rotary evaporator under reduced pressure.[35]
4.2.4 | Synthesis of Fe3O4@SiO2@3‐
glycidoxypropyltrimethoxysilane@
triazole@Pd
Potassium chloride (0.3 g) was dissolved in methanol and
water (1:1, 10 ml) and palladium chloride (0.1 g) was
added to the solution and the mixture was stirred vigor-
ously for 4 h at room temperature. A transparent and
clear reddish solution of [K2PdCl4] was obtained.
Fe3O4@SiO2@triazole was dispersed in methanol
(10 ml) and sonicated for 15 min. Then, the [K2PdCl4]
solution was added and stirred vigorously for 24 h at room
temperature. The resulting catalyst was removed using an
external magnetic field and washed twice with methanol
and dried under vacuum at 40 °C for 10 h.
4.2.2 | Synthesis of Fe3O4@SiO2@3‐
glycidoxypropyltrimethoxysilane@
triazole@cu
4.3 | Typical procedure for C–C Suzuki–
Miyaura cross‐coupling reaction
Fe3O4@SiO2@3‐glycidoxypropyltrimethoxysilane@triaz-
ole@Pd (1.2 mmol% based on Pd, 10 mg) was added to a
mixture of phenylboronic acid (0.6 mmol), aryl halide
(0.5 mmol) and K2CO3 (0.6 mmol) in water (2 ml) and
stirred for 3 h at 80 °C. The progress of the reaction
completion was followed by TLC (EtOAc–n‐hexane,
10:90). After completion of the reaction, the catalyst was
removed using an external magnetic field and the
products were extracted withy ethyl acetate. The solution
was dried over MgSO4 and the organic solvent was
evaporated with a rotary evaporator.
The crude products were purified by flash chromatog-
raphy with n‐hexane–EtOAc. All products were known
compounds and were identified by comparison of
their physical and spectral data with those reported in
the literature.
The synthesized Fe3O4@SiO2 magnetic nanoparticles
(2 g) were sonicated for 30 min in 10 ml of toluene. Then,
3‐glycidoxypropyltrimethoxysilane (11.32 mmol, 2.5 ml)
was added to the mixture while stirring and the mixture
was refluxed for 48 h. The precipitate was washed with
methanol (3 × 30 ml) and dried using a rotary evaporator
under reduced pressure. Sodium azide (22.7 mmol, 1.5 g),
copper(II) chloride (0.74 mmol, 0.1 g) and sodium
ascorbate (0.76 mmol, 0.15 g) were dissolved in a mixture
of tetrahydrofuran (THF) and water (80/20) in a round‐
bottom flask equipped with a magnetic stirring bar. Then,
the modified magnetic nanoparticles (1.0 g) and
phenylacetylene (18.2 mmol, 2 ml) were successively
added to the mixture and stirred at 60 °C for 10 h. By
applying an external magnet, the final product was

DADRAS ET AL.
9 of 9
1
58
2
59
[19] A. Pourjavadi, A. Motamedi, Z. Marvdashti, S. H. Hosseini,
4.4 | Recycling of catalyst
3
60
Catal. Commun. 2017, 97, 27.
4
61
In order to reuse the catalyst, the magnetic Pd(II) catalyst
was collected using an external magnet, washed twice
with methanol and air‐dried overnight.
[20] S. Asadi, R. Sedghi, M. M. Heravi, Catal. Lett. 2017, 147, 2045.
[21] M. O. Sydnes, Catalysts 2017, 7, 35.
5
62
6
63
[22] J. Song, Y. Li, W. Sun, C. Yi, H. Wu, H. Wang, K. Ding, K. Xiao,
7
64
C. Liu, New J. Chem. 2016, 40, 9030.
8
65
ACKNOWLEDGEMENTS
[23] R. N. Baig, R. S. Varma, Chem. Commun. 2013, 49, 752.
9
66
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
67
[24] A. Ghorbani‐Choghamarani, B. Tahmasbi, N. Noori, R.
Ghafouri‐nejad, J. Iran. Chem. Soc. 2017, 14, 681.
We acknowledge the support from Iran University of
Science and Technology (IUST) and Sharif University
of Science and Technology (SUT).
68
69
[25] H. Khojasteh, V. Mirkhani, M. Moghadam, S. Tangestaninejad,
I. Mohammadpoor‐Baltork, J. Iran. Chem. Soc. 2017, 14, 1139.
70
71
[26] M. Gómez‐Martínez, A. Baeza, D. A. Alonso, Catalysts 2017, 7, 94.
ORCID
72
[27] A. Ghorbani‐Choghamarani, B. Tahmasbi, N. Noori, S. Faryadi,
C. R. Chim. 2017, 20, 132.
73
M. Reza Naimi‐Jamal
http://orcid.org/0000-0002-8305-
74
[28] J. Xiao, Z. Lu, Y. Li, Ind. Eng. Chem. Res. 2015, 54, 790.
7234
75
[29] J. Xiao, Z. Lu, Z. Li, Y. Li, Appl. Organomet. Chem. 2015, 29,
Firouz Matloubi Moghaddam http://orcid.org/0000-0002-
8418-9888
76
646.
77
[30] M. Pourkhosravani, S. Dehghanpour, F. Farzaneh, Catal. Lett.
2016, 146, 499.
78
REFERENCES
79
[31] D. A. Safin, M. G. Babashkina, Catal. Lett. 2009, 130, 679.
[32] A. Fürstner, A. Leitner, Synlett 2001, 0290.
80
[1] S. Wittmann, A. Schätz, R. N. Grass, W. J. Stark, O. Reiser,
81
Angew. Chem. Int. Ed. 2010, 49, 1867.
[33] C. Zhang, M. L. Trudell, Tetrahedron Lett. 2000, 41, 595.
[34] M. Zhu, G. Diao, J. Phys. Chem. C 2011, 115, 24743.
82
[2] J. M. Basset, C. Coperet, D. Soulivong, M. Taoufik, J. T. Cazat,
83
Acc. Chem. Res. 2009, 43, 323.
[35] A. Pourjavadi, S. H. Hosseini, S. T. Hosseini, S. A.
84
[3] M. B. Gawande, P. S. Branco, R. S. Varma, Chem. Soc. Rev. 2013,
42, 3371.
Aghayeemeibody, Catal. Commun. 2012, 28, 86.
85
[36] F. M. Moghaddam, S. E. Ayati, RSC Adv. 2015, 5, 3894.
86
[4] M. B. Gawande, A. K. Rathi, P. S. Branco, R. S. Varma, Appl.
Sci. 2013, 3, 656.
[37] A. S. Singh, R. S. Shelkar, J. M. Nagarkar, Catal. Lett. 2015, 145,
87
723.
88
[5] A. Corma, H. Garcia, Top. Catal. 2008, 48, 8.
[38] G. Lv, W. Mai, R. Jin, L. Gao, Synlett 2008, 9, 1418.
89
[6] D. Zhang, C. Zhou, Z. Sun, L. Z. Wu, C. H. Tung, T. Zhang,
90
[39] S. Shylesh, L. Wang, W. R. Thiel, Adv. Synth. Catal. 2010, 352,
Nanoscale 2012, 4, 6244.
425.
91
[7] R. Schlögl, S. B. Abd Hamid, Angew. Chem. Int. Ed. 2004, 43,
[40] M. Beygzadeh, A. Alizadeh, M. M. Khodaei, D. Kordestani,
92
1628.
Catal. Commun. 2013, 32, 86.
93
[8] L. H. Reddy, J. L. Arias, J. Nicolas, P. Couvreur, Chem. Rev.
2012, 112, 5818.
94
[41] C. Bai, Q. Zhao, Y. Li, G. Zhang, F. Zhang, X. Fan, Catal. Lett.
2014, 144, 1617.
95
[9] A. T. Bell, Science 2003, 299, 1688.
96
[42] P. Wang, H. Zhu, M. Liu, J. Niu, B. Yuan, R. Li, J. Ma, RSC Adv.
2014, 4, 28922.
[10] G. A. Somorjai, H. Frei, J. Y. Park, J. Am. Chem. Soc. 2009, 131,
97
16589.
98
[11] B. C. Ranu, K. Chattopadhyay, L. Adak, A. Saha, S. Bhadra, R.
99
SUPPORTING INFORMATION
Dey, D. Saha, Appl. Chem. 2009, 81, 2337.
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
[12] J. A. Melero, R. van Grieken, G. Morales, Chem. Rev. 2006, 106,
Additional Supporting Information may be found online
in the supporting information tab for this article.
3790.
[13] V. Polshettiwar, R. S. Varma, Green Chem. 2010, 12, 743.
[14] A. H. Lu, E. E. Salabas, F. Schüth, Angew. Chem. Int. Ed. 2007,
46, 1222.
How to cite this article: Dadras A, Naimi‐Jamal
MR, Moghaddam FM, Ayati SE. Suzuki–Miyaura
coupling reaction in water in the presence of robust
palladium immobilized on modified magnetic
Fe3O4 nanoparticles as a recoverable catalyst. Appl
Organometal Chem. 2017;e3993. https://doi.org/
10.1002/aoc.3993
[15] L. D. Pachón, G. Rothenberg, Appl. Organomet. Chem. 2008, 22,
288.
[16] B. Karimi, F. Mansouri, H. M. Mirzaei, ChemCatChem 2015, 7,
1736.
[17] M. Kertesz, C. H. Choi, S. Yang, Chem. Rev. 2005, 105, 3448.
[18] O. Baudoin, M. Cesario, D. Guenard, F. Guéritte, J. Org. Chem.
2002, 67, 1199.