Novel palladium nanoparticles supported on β-cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross-coupling reaction with two different approaches in bio-based solvents

Article abstract of DOI:10.1002/aoc.4632

A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M-GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β-cyclodextrin (β-CD) was treated with acryloyl chloride to provide a modified β-CD. Then, in the presence methylenebisacrylamide as a cross-linker, monomers of modified β-CD and acrylamide were polymerized on the surface of the pre-prepared M-GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross-coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross-coupling reactions of N-acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio-based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.

Full text of DOI:10.1002/aoc.4632

Received: 24 July 2018
DOI: 10.1002/aoc.4632
Revised: 14 September 2018
Accepted: 17 September 2018
F U L L P A P E R
Novel palladium nanoparticles supported on β‐
cyclodextrin@graphene oxide as magnetically recyclable
catalyst for Suzuki–Miyaura cross‐coupling reaction with
two different approaches in bio‐based solvents
1
1
2
2
Bahareh Heidari | Majid M. Heravi
| Mohammad Reaz Nabid | Roya Sedghi |
3
Seyyed Emad Hooshmand
1
Department of Chemistry, Alzahra
A novel nanocatalyst was designed and prepared. Initially, the surface of mag-
netic graphene oxide (M‐GO) was modified using thionyl chloride,
tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which pro-
vide reactive C═C bonds for the polymerization of vinylic monomers. Sepa-
rately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a
modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐
linker, monomers of modified β‐CD and acrylamide were polymerized on the
surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium boro-
hydride were added to this composite to afford supported palladium nanoparti-
cles. This fabricated nanocomposite was fully characterized using various
techniques. The efficiency of this easily separable and reusable heterogeneous
catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions
of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐
coupling reactions of N‐acylsuccinimides and boronic acid in green media. The
results showed that the nanocatalyst was efficient in coupling reactions for direct
formation of the corresponding biphenyl as well as benzophenone derivatives in
green media based on bio‐based solvents. In addition, the nanocatalyst was easily
separable, using an external magnet, and could be reused several times without
significant loss of activity under the optimum reaction conditions.
University, Vanak, Tehran, Iran
2
Department of Polymer and Materials
Chemistry, Faculty of Chemistry and
Petroleum Sciences, Shahid Beheshti
University, GC, 1983969411 Tehran, Iran
3
Department of Organic Chemistry and
Oil, Faculty of Chemistry and Petroleum
Sciences, Shahid Beheshti University, GC,
1983969411 Tehran, Iran
Correspondence
Majid M. Heravi, Department of
Chemistry, Alzahra University, Vanak,
Tehran, Iran.
Email: mmheravi@alzahra.ac.ir;
mmh1331@yahoo.com
Roya Sedghi, Department of Polymer and
Materials Chemistry, Faculty of Chemistry
and Petroleum Sciences, Shahid Beheshti
University, GC, 1983969411, Tehran, Iran.
Email: r_sedghi@sbu.ac.ir
Funding information
Alzahra University Research Council; Iran
National Science Foundation
KEYWORDS
bio‐based solvents, host–guest interaction, magnetic graphene oxide (M‐GO), palladium
nanoparticles, Suzuki–Miyaura cross‐coupling reaction
1
| INTRODUCTION
drugs and precursors in the total synthesis of natural prod-
[
12–15]
ucts.
In 2016, Weires et al. reported a modified nickel‐
Palladium‐catalysed Suzuki–Miyaura cross‐coupling reac-
catalysed Suzuki–Miyaura coupling of amides and boronic
[
16]
tion is one of the most powerful and versatile methods for
acid.
It was followed and supported by another report,
[1–11]
the formation of C─C bonds.
It can be applied in the
showing the application of N‐acylsuccinimides as twist‐
controlled, acyl‐transfer reagents in Suzuki–Miyaura
synthesis of a great variety of complex organic molecules,
heterocyclic agrochemicals, pharmaceutical intermediates,
[17]
cross‐coupling reaction via N─C amide bond activation.
Appl Organometal Chem. 2018;e4632.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
1 of 13
https://doi.org/10.1002/aoc.4632

2
of 13
HEIDARI ET AL.
Cross‐coupling reactions are frequently utilized for the syn-
thesis of pharmaceuticals, agrochemicals and polymers.
Although, homogeneous Pd‐based catalyst systems often
much attention of synthetic organic chemists. It is actually
a
cyclic oligosaccharide composed of seven α‐D‐
glucopyranoside units linked together creating a cone
shape with a hydrophobic inner cavity and a hydrophilic
outer surface. This unique and particular structure makes
it an ideal candidate for interaction with many organic
compounds as guests, forming enclosure complexes via a
[18–20]
offer higher activities for these transformations,
they
suffer from problems such as separation of catalyst from
reaction mixture, catalyst recovery and catalyst reusability.
These are serious drawbacks especially when expensive
ligands and metal complexes are used in chemical industry.
Thus, recent advances in ‘green’ reactions have focused on
the design and synthesis of catalysts that are easily separa-
[
54–57]
stable host–guest relationship.
The applications of β‐
CD for organic synthesis as well as its importance as a phase
[58]
transfer agent in catalysis have been well recognized.
We are interested in the Suzuki–Miyaura cross‐
[21–24]
ble,
showing simplified product separation, present-
[
14,59]
ing higher turnover frequencies (TOFs) and turnover
numbers (TONs) and being used under the conditions
coupling reaction,
and also focused on Pd‐ and Pd
nanoparticle‐catalysed reactions, performing them under
[25]
[60,61]
[62–65]
required for sustainable green chemistry. In this regard,
heterogeneous conditions
using β‐CD
and
a wide variety of alternative methods for heterogeneous Pd‐
have experience in activation of carbon heteroatoms
catalysed by nickel.
[26]
[66]
catalysed Suzuki reactions have been introduced. Signif-
icantly, for the preparation of various Pd species as hetero-
geneous catalysts, they have been immobilized onto
In addition to synthetic organic solvents, nature pro-
vides some materials such water as the most abundant
and greenest solvent. Water as a green solvent and plen-
tiful resource also shows admirable specificity and thus
has been used in a plethora of chemical processes. Nowa-
[
27–30]
[31]
poly(amido‐amine) dendrimers,
vinylpyrrolidone,
polypyrrole, poly-
[32]
[33]
poly(p‐phenylene ethynylene),
polyaminoacetanilide composite,
polystyrene–polyethylene glycol,
[34]
[35]
[37]
Wang resin,
polystyrene–DVB,
[36]
days, an extensive investigation of the application of
[38]
[39]
[67]
polystyrene resin
and Merrifield resin,
each having
biomass‐derived solvents is also underway.
Biomass
its own merits and drawbacks. As a weakness, all of them
have their catalytic active sites spread in all the regions of
the resin, including the interior, and therefore it is difficult
for the reagents to diffuse into the interior of the resin, thus
feedstocks of plant and algal origin are green and readily
accessible materials, and can be converted into fuels like
ethanol, butanol, biodiesel and other hydrocarbon fuels.
In this context, several biomass‐derived solvents are
industrially provided and are commercially available.
They are ethanol, glycerol, ethyl lactate and cyrene. On
the other hand, deep eutectic solvent (DES) systems
based on choline chloride and glycerol or urea as green
[38]
the overall reaction rate is decreased.
For the improve-
ment of the applicability of these Pd species, various poly-
mers have been functionalized before being used as
supports. Recently, many ongoing attempts have been
focused on deposition of various nanoparticles on graphene
[
68]
media have become available in recent years.
Choline
[
40–42]
oxide (GO) sheets due to the superior functionality
and excellent mechanical, electronic, optical and thermal
chloride as a natural biocompatible compound is pro-
duced on large scale to provide chicken feed additive.
Stimulated by the facts and concerns mentioned above,
herein, we report the design, preparation and characteriza-
tion of M‐GO/(AM‐MBA‐β‐CD@Pd) (M‐GO, magnetic GO;
AM, acrylamide; MBA, methylenebisacrylamide) nanocom-
posite and its application as an efficient and recyclable cata-
lyst for the Suzuki–Miyaura cross‐coupling reactions of aryl
halides with boronic acids as well as for modified Suzuki–
Miyaura cross‐coupling reactions of N‐acylsuccinimides
and boronic acid in green media (Figure 1 and Scheme 1).
[43,44]
properties.
GO has a unique atom‐thick two‐
dimensional sheet structure consisting of hydrophilic oxy-
gen functional groups such as epoxy bridges, carbonyl and
hydroxyl groups. Such sheets can be chemically functional-
ized to provide graphene‐based composites.
Designing water‐soluble immobilized catalysts has
received much attention in organic cross‐coupling reac-
tions. Popular strategies for the Suzuki–Miyaura reaction
in water have been developed including addition of organic
[
45]
co‐solvents,
being performed under microwave irradia-
[
46]
[47]
tion and ultrasonic irradiation, ligand‐free methodol-
[
48]
[49]
ogy,
using surfactants
and the modification of the
2 | EXPERIMENTAL
catalyst with water‐soluble functional groups such as
[50]
[51]
polyoxyethylene moieties
and sulfonate,
ammo-
2.1 | Reagents and materials
[52]
[53]
nium and carboxylate groups. Notably, conventional
nanocatalysts show some drawbacks such as poor solubility
of aryl halide in aqueous media and low capacity for
increasing the efficiency of reaction. Recently, β‐
cyclodextrin (β‐CD) as a hydrophilic molecule has attracted
Graphite powder, potassium persulfate, acrylamide,
methylenebisacrylamide, azobisisobutyronitrile, FeCl3⋅
6H O, FeCl ⋅4H O, H SO (98%), HNO (65%) and NH OH
2
2
2
2
4
3
4
(28%) were purchased from Merck. Pd(OAc) , boronic
2

HEIDARI ET AL.
3 of 13
FIGURE 1 Schematic of M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite
acids, variously substituted aryl halides and β‐CD were pur-
chased from Sigma‐Aldrich. All employed solvents, ini-
tially, were dried using standard processes and freshly
distilled prior to use.
2.2.1 | Synthesis of M‐GO/(AM‐MBA‐β‐
CD@Pd) nanocomposite
The detailed synthesis of the M‐GO/(AM‐MBA‐β‐
CD@Pd) nanocomposite is described step by step in the
supporting information. GO sheets were prepared via a
[
69]
modified Hummers method.
2.2 | Instrumentation
2.3 | Preparation of DES
Fourier transform infrared (FT‐IR) spectra were recorded
using a BOMEM MB series spectrometer in the form of
−
1
A choline chloride‐based DES was prepared according to
KBr pellets over the range 400–4000 cm . For determi-
nation of Pd loaded on the nanocomposite, a Shimadzu
model AA‐680 atomic absorption spectrometer with air–
acetylene flame atomizer and hollow cathode lamp was
used. A scanning electron microscopy (SEM) instrument
[
70]
a procedure reported in the literature.
Accordingly,
choline chloride with urea, ethylene glycol and glycerol
were mixed and heated at 80°C until the formation of a
liquid. The obtained DES was used without any further
purification.
(Philips XL‐30) was used for investigation of surface mor-
phological features and size of the nanocatalyst. In order
to obtain more quantitative data of the surface of the
nanocatalyst, a transmission electron microscopy (TEM)
instrument (Philips CM‐30) was employed. The progress
of the cross‐coupling reactions was monitored using GC
with a Shimadzu instrument. The crystalline phases of
the nanocatalyst were investigated using X‐ray diffraction
2
.4 | Suzuki–Miyaura reaction catalysed
by M‐GO/(AM‐MBA‐β‐CD@Pd)
nanocomposite: general procedure
In a typical experiment, an appropriate aryl halide
(
1 mmol), arylboronic acid (1.2 mmol), K CO (3 mmol),
2
3
(
8
XRD) measurements (diffraction angle (2θ) from 10° to
0° with a Siemens D5000 X‐ray diffractometer). The
GO/(AM‐MBA‐β‐CD@Pd)
nanocomposite
(0.008–
0.1 mol%) and water (6 ml) were placed in a 50 ml
magnetic properties of the synthesized nanocomposite
were analysed using vibrating sample magnetometry
round‐bottom flask. The reaction mixture was stirred
for various times (2–5 h) and at various temperatures
(40–80°C) depending on each particular substrate. Upon
completion of the reaction (monitored by GC), the
(VSM) with a DC magnetometer (1.5 T, Imax = 150 A,
P ≤ 9 kW) at room temperature.

4
of 13
HEIDARI ET AL.
SCHEME 1 Synthesis route of M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite
mixture was cooled to ambient temperature (25°C).
Then, the solution was diluted with distilled water–ethyl
acetate and the catalyst was separated from the reaction
mixture using a magnet bar. The filtrate was extracted
with ethyl acetate, and the organic phase was separated,
dried over MgSO4, left for a while and then filtered off.
The organic solvent was evaporated to dryness under
reduced pressure to give a crude material. The residue
was purified by column chromatography (ethyl
acetate–n‐hexane) to give the pure corresponding prod-
uct. All compounds were known and identified by com-
parison of their physical and spectroscopic data with
those of authentic samples, which were found to be
identical.
2.5 | Synthesis of benzophenones from
reaction of N‐acylsuccinimides and boronic
acid: general procedure
An appropriate N‐acylsuccinimide (1; 0.5 mmol), synthe-
sized according to a previously reported procedure,
[71]
and 0.6 mmol of phenylboronic acid 2 were added to a
10 ml round‐bottom flask fitted with a magnetic stirrer
containing a suspension of catalyst (0.03 mol%) in 2 ml
of DES (choline chloride–glycerol, 1:2). The resultant
mixture was vigorously stirred at 90°C for 5 h. The prog-
ress of the reaction was monitored by TLC (ethyl
acetate–n‐hexane). After completion of the reaction, the
mixture was cooled to room temperature. Then, water

HEIDARI ET AL.
5 of 13
(
5 ml) was added to this mixture, the nanocatalyst was
of these bands confirmed the successful linkage of
acryloyl chloride to β‐CD. The spectrum of the final
polymeric nanocomposite (Figure 2f) showed bands at
1639 and 3300 cm which can be assigned to CONH2
and NH groups, respectively.
separated using an external magnet and then ethyl ace-
tate was added (5 ml). The residue was purified by col-
umn chromatography (ethyl acetate–n‐hexane) to afford
the pure corresponding products 3a–f.
−
1
3
.1.2 | NMR spectroscopic analysis
3
3
3
| RESULTS AND DISCUSSION
Functionalized β‐CD was used as a monomer in the
structure of the catalyst. This applied monomer shows a
dual role (inclusion of complex and providing hydrophilic
properties). The functionalized β‐CD monomer was pro-
duced using acryloyl chloride, in which one of the pri-
mary ─OH groups of β‐CD was reacted with the
carbonyl group of acryloyl chloride. The NMR analysis
of the product illustrated the functionalization of β‐CD
.1 | Characterization
.1.1 | FT‐IR spectroscopic analysis
FT‐IR analysis was successfully applied to investigate the
presence of functional groups in the synthesized com-
pounds. The FT‐IR spectrum of GO (Figure 2a) exhibited
−
1
the main absorption bands at 1721, 1618 and 3400 cm
(
Figure 1 in supporting information).
that are assigned to C═O stretching vibration, C═C of
aromatic ring and ─OH groups of GO, respectively.
According to Figure 2b (spectrum of M‐GO), the band
at 553 cm is attributed to Fe─O stretching vibration.
After modification of M‐GO with tris(hydroxymethyl)
aminomethane (Figure 2c), the appearance of the band
3.1.3 | XRD analysis
−
1
XRD patterns of prepared GO, M‐GO and the M‐
GO/(AM‐MBA‐β‐CD) nanocomposite are depicted in
Figure 3. The sharp characteristic GO peak at around
10.6° is attributed to the (002) plane of GO sheets and
−
1
at around 1695 cm
vibration. In the spectrum of acrylate‐modified GO
is due to the amide carbonyl
(
1
1
Figure 2d), the C═O stretching band at around
another peak at 42.2° corresponds to the (001) reflection
−
1
[72–74]
731 cm
and the C─O stretching band at
plane of GO.
In comparison with the pattern of pure
−
1
200 cm are characteristic for ester bonds, indicating
graphite which is dominated by an intense peak at
2θ = 26.48° corresponding to reflection in (002) planes
of well‐ordered graphene layers, a graphene peak (26.4°)
the successful linkage of acryloyl chloride to the
surface of amine‐modified M‐GO. The spectrum of
vinyl‐modified β‐CD (Figure 2e) exhibited peaks at
can be attributed to a very small concentration of non‐
−
1
[75]
1
731 and 1029 cm
which were assigned the C═O
oxidized graphene.
According to the type of sample
and C─O stretching bands, respectively. Appearance
holder, the peak at 2θ = 63° is attributed to the duplex
[
76]
stainless steel of the analytical apparatus
(Figure 3a).
Interestingly, the XRD pattern of the M‐GO hybrid
indicated the presence of a similar crystalline structure
of pure Fe O4 at 2θ = 30.22°, 35.59°, 43.29°, 53.69°
3
and 62.81° which indicated the structure of Fe O
3
4
FIGURE 2 FT‐IR spectra of (a) GO, (b) M‐GO, (c) amine group‐
modified GO, (d) vinyl group‐modified GO, (e), acrylated β‐CD and
FIGURE 3 XRD patterns of (a) GO, (b) M‐GO and (c) M‐GO/
(AM‐MBA‐β‐CD) nanocomposite
(
f) M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite

6
of 13
HEIDARI ET AL.
nanoparticles (Figure 3b). Nevertheless, the diffraction
peak (2θ ~ 10.8°) of GO totally disappeared in the pattern
of the M‐GO hybrid, which most probably is due to the
exfoliation/distortion of GO bundles, when they are
successfully loaded onto the surface of M‐GO/(AM‐
MBA‐β‐CD). The high density of polymeric backbones
prevents the agglomeration of Pd nanoparticles on the
GO sheets.
[77]
ground with Fe O .
The XRD pattern of the M‐
3
4
GO/(AM‐MBA‐β‐CD) nanocomposite showed a broad
diffraction peak at 2θ = 10–28° assigned to the scattering
of amorphous polymeric skeleton (Figure 3c).
3
.1.5 | X‐ray photoelectron spectroscopy
(XPS)
XPS was applied to investigate the electronic state of Pd
species that exist within the catalyst. As shown in Figure
3.1.4 | SEM and TEM images
2
in the supporting information, the binding energies of
Pd 3d in the catalyst were 335.48 and 340.94 eV which
The morphologies of GO sheets and the final nanocom-
posite are demonstrated in Figure 4A,B. The SEM image
of GO shows a homogeneous and smooth coating layer
with a size of several micrometres (Figure 4A). In com-
parison to GO, the SEM image of the M‐GO/(AM‐
MBA‐β‐CD@Pd) nanocomposite (Figure 4B) shows
spherical polymeric particles on the surface of GO sheet.
The results confirmed the successful polymerization of
monomers as a shell on M‐GO sheet. The distribution of
Pd nanoparticles onto the surface of M‐GO was character-
ized by cross‐sectional TEM imaging of the final nano-
composite (Figure 4C,D). According to the TEM images,
round‐shaped structures of the Pd nanoparticles are
clearly observed, indicating that Pd nanoparticles were
0
[78,79]
are ascribed to Pd 3d5 and 3d3/2, respectively.
/2
3.1.6 | VSM analysis
The magnetic properties of the final nanocomposite were
investigated using VSM. According to Figure 3 in the
supporting information, the magnetization curves are
symmetric and pass through the origin. These observa-
tions showed no remanence and coercivity, indicating
the supermagnetic behaviour of the nanocatalyst. The
−
1
value of magnetic saturation (M ) is around 10 emu g ,
s
far less than that of pure Fe O due to the presence of
3
4
the polymeric shell on the surface of M‐GO sheets.
FIGURE 4 SEM images of (a) GO and (b) M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite. TEM images of (c) GO and (d) M‐GO/(AM‐
MBA‐β‐CD@Pd) nanocomposite

HEIDARI ET AL.
7 of 13
However, this magnetic property of the nanocomposite
was sufficient for efficient magnetic separation (collected
in less than 60 s using an external magnetic field).
often need to be performed under harsh reaction condi-
tions. Here, water plays a dual role, as a medium and
co‐catalyst due to its high surface tension and hydropho-
[
85]
bic nature. The hydrophobic effect emphasizes the ten-
dency of nonpolar molecules or their surfaces to
aggregate in water. According to Breslow, for the hydro-
phobic effect in water, the substrates are forced to form
aggregates in order to decrease the exposed organic sur-
3
.2 | Catalytic performance of final
magnetic nanocomposite
[
86]
Pd nanoparticles immobilized onto polymers have been
face area.
When a salt or polar molecules is dissolved
extensively employed in various cross‐coupling reac-
or dispersed in water, the hydrophobic effect is increased.
In this research, at first, we successfully examined the
[80,81]
tions.
Nonetheless, there are just a few reports of
the utilization of magnetically separable nanoparticles
Suzuki–Miyaura
cross‐coupling
reaction
of
stabilized by hydrophilic polymers for catalysed cross‐
coupling reactions under eco‐friendly conditions.
bromobenzene with phenylboronic acid in the presence
of our novel designed, prepared and fully characterized
Pd‐based nanocatalyst in water as a green solvent as a
model reaction (Table 1). The use of water as the solvent
provides excellent interaction between the heterogeneous
stabilized Pd nanocomposite and hydrophilic (boronic
acid) and hydrophobic (aryl halide) species which conse-
quently resulted in an increase in the yield and rate of the
cross‐coupling reaction. The amount of catalyst used and
time of the reaction are two significant parameters which
were carefully studied in this work. The best conversion
occurred in the above‐mentioned model reaction when
the substrate was reacted in the presence of 0.01 mol%
of catalyst in 3 h, providing the corresponding biphenyl
in satisfactory yield (Table 1).
[82–84]
In this work we examined the catalytic activity of our
novel and easily separable M‐GO/(AM‐MBA‐β‐CD@Pd)
nanocomposite in Suzuki–Miyaura cross‐coupling reac-
tions under eco‐friendly conditions. The flexibility in sur-
face functionalities, large surface area to volume ratio and
superior mechanical performance of the M‐GO/(AM‐
MBA‐β‐CD@Pd) nanocomposite had a great impact on
the amount of catalyst loaded and decreased the required
reaction time significantly. The heterogeneous Suzuki–
Miyaura cross‐coupling process has been generally inves-
tigated using aryl iodides as reactive substrates, which are
rather expensive. Utilization of aryl bromides as substrate
instead of aryl iodides in Suzuki–Miyaura cross‐coupling
reactions is more desirable from an economic point of
view for large‐scale synthesis. Meanwhile, activation of
aryl chlorides as reactants is extremely challenging
because of the higher bond strength of aryl moiety with
chloride. Thus, Suzuki–Miyaura cross‐coupling reactions
of aryl chlorides with an appropriate boronic acid partner
Table 2 presents the corresponding biaryls as coupled
products, obtained from the reaction of variously
substituted boronic acids with a variety of aryl halides.
As is evident, iodobenzene, 4‐iodotoluene and 4‐
iodoanisole gave the corresponding biaryls in the pres-
ence of 0.008 mol% catalyst in only 2 h (Table 2, entries
TABLE 1 Optimization of reaction conditions for Suzuki–Miyaura reaction of bromobenzene with phenylboronic acid catalysed by M‐GO/
a
(
AM‐MBA‐β‐CD@Pd) nanocomposite
b
Entry
Amount of catalyst (mol%)
Temp. (°C)
Solvent
Time (h)
Conversion (%)
1
3
4
5
6
7
8
9
0.1
80
80
80
70
70
70
50
50
50
40
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
O
O
O
O
O
O
O
O
O
O
8
8
6
5
3
3
3
3
3
3
100
100
100
100
100
100
100
100
96
0.05
0.05
0.05
0.05
0.02
0.02
0.01
0.008
0.01
1
0
1
1
98
a
Reaction conditions: phenylboronic acid (1.2 mmol), bromobenzene (1 mmol), K
6 ml).
2 3 2
CO (3 mmol), M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite as catalyst, H O
(
b
Calculated by GC.

8
of 13
HEIDARI ET AL.
TABLE 2 Suzuki–Miyaura reaction of various aryl halides with arylboronic acids catalysed by M‐GO/(AM‐MBA‐β‐CD@Pd)
a
nanocomposite
b
Entry
R
1
R
2
X
Amount of catalyst (mol%) Time (h) Temperature (°C) Conversion (%)
TOF TON
1
2
3
4
5
6
7
8
9
H
H
I
I
I
0.008
0.008
0.008
2
2
2
3
3
3
3
5
5
5
2
2
2
3
3
5
5
5
40
40
40
50
50
50
50
60
60
60
40
40
40
50
50
80
80
80
100
100
100
97
6125 12 250
6125 12 250
6125 12 250
4‐Me
4‐OMe
H
H
H
H
Br 0.01
Br 0.01
Br 0.01
Cl 0.01
Cl 0.1
Cl 0.1
Cl 0.1
3033
3066
3000
—
9 099
9 198
9 000
4‐NO
4‐Me
H
2
H
98
H
95
H
NR
67
—
H
H
120
116
126
600
580
630
4‐Me
4‐NO
H
H
62
10
11
12
13
14
15
16
17
18
2
H
70
Me
Me
I
I
I
0.008
0.008
0.008
98
5750 11 500
5687 11 374
5625 11 250
4‐Me
97
4‐OMe Me
96
H
Me Br 0.01
Me Br 0.01
Me Cl 0.1
Me Cl 0.1
95
2966
2933
100
84
8 898
8 799
500
4‐Me
H
94
58
4‐Me
50
420
4‐OMe Me Cl 0.1
45
80
400
a
Reaction conditions: arylboronic acid (1.2 mmol), aryl halide (1 mmol), K
2
CO
3
(2–3 mmol), M‐GO/(AM‐MBA‐CD@Pd) nanocomposite as catalyst, H
2
O (6 ml).
b
Calculated by GC.
1
–3). To establish the general substrate scope, variously
0.01 mol% of our catalyst in water. This reaction proceeded
sluggishly, giving the products after 5 h, but a significant
amount of starting materials remained unreacted in the
reaction mixture. Delightfully, by increasing the amount
of catalyst loading to 0.1 mol% and extending the reaction
time to 5 h at 60°C, our model reaction completed, giving
rise to the corresponding product in satisfactory yield
(entry 8). Encouraged by this result, the Suzuki–Miyaura
cross‐coupling reactions of aryl chlorides with various
boronic acids were performed under identical reaction con-
ditions, leading to the formation of the corresponding
products (entries 9–10, 16–18). Furthermore, 4‐tolylboronic
acid was reacted with various aryl halides under the same
reaction conditions to afford the corresponding products
(entries 11–18). All products were known and identified
by comparison of their physical data (melting points) and
substituted aryl bromides were used. Aryl bromides bear-
ing electron‐donating and electron‐withdrawing groups
gave the corresponding biaryls in excellent yields in the
presence of 0.01 mol% catalyst in only 3 h (Table 2,
entries 4–6). The prepared catalyst efficiently catalysed
the Suzuki cross‐coupling reactions of aryl iodides and
aryl bromides. It has been shown that the Suzuki reaction
does not proceed smoothly when aryl chlorides are used,
these being commonly less reactive than aryl iodides and
aryl bromides in the Suzuki–Miyaura cross‐coupling reac-
tion since a C─Cl bond is stronger than both C─Br and
C─I bonds. Thus, longer reaction times, more active cata-
lyst or higher catalyst loading are required. In fact, aryl
chlorides are more accessible and are commercially less
expensive than their bromo and iodo counterparts. Thus,
employing aryl chlorides in Suzuki–Miyaura cross‐
coupling reactions in at the pilot and even bench scale is
more desirable. Encouraged by the preparation of an
efficient Pd‐based nanocatalyst which fruitfully catalysed
the Suzuki–Miyaura cross‐coupling reaction, we selected
1
spectral data ( H NMR and FT‐IR spectra) with those of
authentic samples and found to be identical.
Encouraged by the results, confirming the high activ-
ity and diversity of the novel M‐GO/(AM‐MBA‐β‐
CD@Pd) nanocomposite in the expeditious synthesis of
biphenyl derivatives in water as a user‐friendly solvent,
we decided to examine its catalytic activity in the
a
model reaction involving chlorobenzene and
phenylboronic acid and reacted them in the presence of

HEIDARI ET AL.
9 of 13
synthesis of benzophenone derivatives (Figure 5) through
cross‐coupling reaction of N‐acylsuccinimides as versatile
acyl‐transfer reagents and phenylboronic acids (modified
Suzuki–Miyaura cross‐coupling reaction). In general, an
amide is not very reactive since its bonds are compara-
tively strong. However, some amides have emerged as
promising precursors for achieving highly selective amide
cross‐coupling reactions, leading to the direct access to
benzophenones via modified Suzuki–Miyaura coupling
reaction. Interestingly, we found that the M‐GO/(AM‐
MBA‐β‐CD@Pd) nanocomposite acted as a robust and
effective catalyst not only in the efficient and facile syn-
thesis of biphenyls via Suzuki–Miyaura cross‐coupling
reactions, but it also plays a significant catalytic role in
the direct synthesis of benzophenones in DES as neoteric
medium in our model reaction involving N‐
acylsuccinimides and phenylboronic acid to give the cor-
responding benzophenone. In order to optimize the reac-
tion conditions, we investigated the effect of various
media such as water, ethanol, tetrahydrofuran and
[
17,87]
benzophenone derivatives, as reported previously.
Inspired by this breakthrough, we investigated the cata-
lytic efficiency of the novel M‐GO/(AM‐MBA‐β‐CD@Pd)
nanocomposite for N‐C bond cleavage to yield
CH CN as well as three other types of DES systems based
3
on choline chloride as hydrogen bond acceptor and urea,
ethylene glycol and glycerol as hydrogen bond donor. The
required amount of catalyst and reaction time for the syn-
thesis of benzophenones from the reaction of N‐
acylsuccinimides and phenylboronic acid were also opti-
mized. As evident from Table 3, higher yield of product
was obtained and shorter reaction time required when
using 0.03 mol% M‐GO/(AM‐MBA‐β‐CD@Pd) nanocom-
posite in choline chloride and glycerol mixture at 90°C
(
Table 3, entry 10). Electron‐withdrawing groups such
as nitro group on N‐acylsuccinimides showed increased
yields in comparison to electron‐donating groups. These
results prompted us to establish our novel catalyst in a
synthetic methodology leading to the straightforward
FIGURE 5 Structure and isolated yields of products
a
TABLE 3 Optimization of reaction conditions for synthesis of benzophenones
b
c
Entry
Solvent
Time (h)
Amount of catalyst (mol%)
Temp. (°C)
Yield (%)
1
2
3
4
5
6
7
8
9
Water
6
6
6
6
6
6
6
6
6
5
4
4
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.02
0.03
0.03
0.03
100
78
80
60
80
90
90
90
90
90
90
75
0
EtOH
Trace
Trace
32
Water–EtOH
Tetrahydrofuran
CH
3
CN
20
ChCl–urea
65
ChCl–ethylene glycol
ChCl–glycerol
ChCl–glycerol
ChCl–glycerol
ChCl–glycerol
ChCl–glycerol
52
78
64
1
1
1
0
1
2
78
72
60
a
2 3
Reaction conditions: 1 (0.5 mmol), 2 (0.6 mmol), K CO (1 mmol).
b
ChCl, choline chloride.
c
Isolated yield.

10 of 13
HEIDARI ET AL.
synthesis of benzophenones under milder reaction condi-
tions. TON and TOF for compound 3d were also deter-
mined to be 2966 and 593, respectively. Using DES as
medium in this catalytic system, in addition to the bene-
fits of the philosophy of green chemistry, leads to prod-
ucts and can also participate in subsequent reactions.
Next, the versatility of the nanocatalyst for amide acyl
N─C bond cross‐coupling process to achieve diverse ben-
zophenones using several reactants was demonstrated
and the results are shown in Figure 5. All the reactants
have been applied successfully in this cross‐coupling
reaction in DES with appropriate yields.
3.3 | Leaching
Another catalytic experiment was further conducted to
estimate the impact of Pd leaching. For this purpose, a
certain amount of the novel catalyst was dispersed in
water (as solvent) in the presence of K CO . The mixture
2
3
was stirred for a particular time and then filtered off to
achieve a transparent solution. In the next step, in accor-
dance with our model reaction, Suzuki–Miyaura coupling
substrates,
namely
phenylboronic
acid
and
bromobenzene, were introduced to the clean supernatant
obtained as described above and this mixture was heated
to 80°C under stirring. We did not observe the formation
of biphenyl even after 5 h, indicating that the coupling
reaction is catalysed by heterogeneous catalysis and is
not a homogeneous type with leaching of Pd.
3.4 | Hot filtration test
FIGURE
6
Reusability
of
M‐GO/(AM‐MBA‐β‐CD@Pd)
nanocomposite catalyst in Suzuki–Miyaura reaction of
bromobenzene with phenylboronic acid
Furthermore, hot filtration test was performed to investi-
gate whether the reaction proceeded in a heterogeneous
TABLE 4 Comparison results of cross‐coupling reaction using M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite as catalyst with previously
reported results
Time Yield (%) or conversion
Entry Catalyst (Pd loading, mol%)
Reaction conditions
(h)
(%)
Ref.
[
[
[
[
[
88]
89]
90]
91]
92]
1
2
5
6
7
8
Poly(NIPAM‐co‐4‐VP)‐Pd (1)
GO‐NH ‐Pd(II) (1)
K
2
K
2
K
2
K
2
K
2
K
2
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
, H
2
O, 60°C
5
4
6
1
95
71
92
95
91
90
2
, EtOH–H
, EtOH–H
, EtOH–H
, EtOH–H
2
2
2
2
O, 60°C
O, 25°C
O, 25°C
Pd@MIL‐101 (0.15)
N‐doped NPC‐Pd (0.2)
N‐doped PC‐900‐Pd (0.2)
O, 25°C 1.5
M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite (0.01)
, H
2
O, 50°C
3
This work
[
[
[
[
93]
89]
94]
95]
9
1
1
1
1
MOF‐5‐NPC‐900‐Pd (0.1)
K
2
2
CO
CO
3
3
, EtOH–H
, EtOH–H
2
O, 25°C
O, 60°C
1
4
98.6
73
0
1
2
3
GO‐NH
Pd/Fe
Pd–Co
2
‐Pd (II) (1)
/G (0.3)
/G (1)
K
2
3
O
4
EtOH–H
EtOH–H
2
2
O, 25°C
45 min 100 conversion
10 min 100 conversion
3
O
4
O, 120°C
O, 50°C
M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite (0.01)
K
2
CO
3
, H
2
3
91
This work
[
96]
1
1
4
5
Pd/CuO (1)
K
2
2
CO
CO
3
3
, EtOH–H
, EtOH–H
2
2
O, 150°C 10 min 90
O, 40°C 98
M‐GO/(AM‐MBA‐β‐CD@Pd) nanocomposite (0.008) K
4
This work

HEIDARI ET AL.
11 of 13
or homogeneous fashion. In a typical experiment, our novel
Pd‐based catalyst (0.01 mol%), bromobenzene (1 mmol),
phenylboronic acid (1.2 mmol) and K CO (3 mmol) were
chloride and glycerol. The novel nanocatalyst with poly-
mer shell due to sharing an electron pair of N and O atoms
of AM and MBA was developed in which Pd nanoparticles
have a better chance of interaction in aqueous media. On
the other hand, β‐CD provides suitable interaction with
aryl halides and N‐acylsuccinimides as guests generating
inclusion complexes via stable host–guest interactions.
This prototype catalyst demonstrated an encouraging level
of catalytic activity in the Suzuki–Miyaura cross‐coupling
reactions of aryl halides including challenging aryl chlo-
rides. More importantly, it uniquely activates the amide
N─C bond for facile cleavage in green media to give ben-
zophenones in high yields. This catalyst can be easily sep-
arated using a magnetic field and can be reused for six runs
without significant loss of activity under optimum reaction
conditions. The separated and reused catalyst needs no
pre‐activation for being used in a subsequent run. The cat-
alyst also showed high TOFs and TONs as two important
green chemistry metrics.
2
3
taken in water in a round‐bottomed flask and stirred at
0°C for 1 h (conversion at 42%). At this stage, the catalyst
5
was separated using a magnet and the experiment was con-
tinued for another 2 h. However, no further progress in the
reaction was observed even after a prolonged reaction time
(monitored by GC). Furthermore, atomic absorption spec-
troscopic analysis did not show any Pd leaching in this
stage. This means that no Pd nanoparticles were leached
into the reaction mixture and the catalytic activity of the
novel catalyst mainly depended on the Pd complex.
3.5 | Reusability and stability of
nanocatalyst
The reusability of the nanocatalyst in the Suzuki–
Miyaura reaction was also investigated by performing
the model reaction. Bromobenzene and phenylboronic
acid were reacted under the already determined opti-
mized reaction conditions. In each cycle, 3 ml of aqueous
solution containing reagents and the catalyst was added
into a 50 ml round‐bottomed flask at optimal tempera-
ture. After completion of the reaction, the nanocatalyst
was separated from the mixture using an external mag-
netic bar, washed with water, dried at room temperature
and reused for the next cycle in the same reaction. As
shown in Figure 6, the nanocatalyst could be reused at least
six times without any appreciable loss in its activity in the
Suzuki–Miyaura cross‐coupling reaction. The remaining
amount of Pd after the sixth cycle was decreased by
ACKNOWLEDGEMENT
The authors are thankful to Alzahra University Research
Council. MMH is also appreciative to Iran National Sci-
ence Foundation (INSF) for the granted research chair.
ORCID
Majid M. Heravi http://orcid.org/0000-0003-2978-1157
Seyyed Emad Hooshmand
573-5539
http://orcid.org/0000-0001-
5
−1
−1
REFERENCES
0
.250 mmol g to 0.235 mmol g as determined using
atomic absorption spectroscopic analysis (6% leaching).
[1] M. M. Heravi, E. Hashemi, Tetrahedron 2012, 68, 9145.
[
2] L. Yizhu, L. Guosong, Z. Dajian, W. Renshu, Z. Xiao‐Yu, L.
Guangxing, Appl. Organometal. Chem. 2018, 32, e4421.
https://doi.org/10.1002/aoc.4421
3.6 | Comparison
[
3] N. Mohsen, G. Farshid, G.‐C. Arash, E. Zahra, Appl.
Organometal. Chem. 2018, 32, e4282. https://doi.org/10.1002/
aoc.4282
To evaluate the efficiency of the M‐GO/(AM‐MBA‐β‐
CD@Pd) nanocomposite, its catalytic activity was com-
pared to those reported in previous literature. As evident
from Table 4, the M‐GO/(AM‐MBA‐β‐CD@Pd) nanocom-
posite is a superior nanocatalyst in terms of using green
[
[
[
[
4] H. Veisi, M. Pirhayati, A. Kakanejadifard, Tetrahedron Lett.
2017, 58, 4269.
5] H. Veisi, N. Mirzaee, Appl. Organometal. Chem. 2018, 32,
e4067.
[88–96]
conditions, reaction time and also isolated yield.
6] H. Veisi, S. Najafi, S. Hemmati, Int. J. Biol. Macromol. 2018,
113, 186.
4
| CONCLUSIONS
7] H. Veisi, M. Pirhayati, A. Kakanejadifard, P. Mohammadi, M.
Our investigations demonstrate that the immobilization of
Pd nanoparticles on M‐GO/(AM‐MBA‐β‐CD) nanocom-
posite produces a well‐defined and superior catalyst for
Suzuki–Miyaura cross‐coupling reactions in water as well
as bio‐based solvents such as DESs based on choline
R. Abdi, J. Gholami, S. Hemmati, Chem. Sel. 2018, 3, 1820.
[8] H. Veisi, P. M. Biabri, H. Falahi, Tetrahedron Lett. 2017, 58,
3482.
[9] H. Veisi, S. A. Mirshokraie, H. Ahmadian, Int. J. Biol.
Macromol. 2018, 108, 419.

12 of 13
HEIDARI ET AL.
[
10] F. Heidari, M. Hekmati, H. Veisi, J. Colloid Interface Sci. 2017,
01, 175.
[41] C. Zhu, S. Dong, Nanoscale 2013, 5, 1753.
5
[42] E. Vessally, A. Hassanpour, R. Hosseinzadeh‐Khanmiri, M.
[
[
[
11] E. Farzad, H. Veisi, J. Ind. Eng. Chem. 2018, 60, 114.
Babazadeh, J. Abolhasani, Monatsh. Chem. 2017, 148, 321.
12] R. Chinchilla, C. Nájera, Chem. Rev. 2007, 107, 874.
[43] D. A. Dikin, S. Stankovich, E. J. Zimney, R. D. Piner, G. H.
Dommett, G. Evmenenko, S. T. Nguyen, R. S. Ruoff, Nature
13] H. U. Blaser, A. Indolese, F. Naud, U. Nettekoven, A. Schnyder,
2007, 448, 457.
Adv. Synth. Catal. 2004, 346, 1583.
[
44] A. Hosseinian, A. Amjad, R. Hosseinzadeh‐Khanmiri, E.
Ghorbani‐Kalhor, M. Babazadeh, E. Vessally, J. Mater. Sci.
Mater. Electron. 2017, 28, 18040.
[
[
14] T. K. K. Afsaneh, H. M. M., M. Tayebeh, Appl. Organometal.
Chem. 2018, 32, e4210 https://doi.org/10.1002/aoc.4210.
15] M. König, L. M. Reith, U. Monkowius, G. Knör, K.
[
[
[
45] F. Li, T. Hor, Adv. Synth. Catal. 2008, 350, 2391.
Bretterbauer, W. Schoefberger, Tetrahedron 2011, 67, 4243.
46] D. Dallinger, C. O. Kappe, Chem. Rev. 2007, 107, 2563.
[
16] N. A. Weires, E. L. Baker, N. K. Garg, Nat. Chem. 2016, 8, 75.
17] Y. Osumi, C. Liu, M. Szostak, Org. Biomol. Chem. 2017, 15,
47] A. L. F. de Souza, L. C. da Silva, B. L. Oliveira, O. Antunes, Tet-
rahedron Lett. 2008, 49, 3895.
[
8
867.
[
48] M. Nasrollahzadeh, S. Mohammad Sajadi, J. Colloid Interface
Sci. 2016, 465, 121. https://doi.org/10.1016/j.jcis.2015.11.038
[
[
18] S. Gupta, B. Basu, S. Das, Tetrahedron 2013, 69, 122.
19] Y.‐Q. Tang, H. Lv, J.‐M. Lu, L.‐X. Shao, J. Organometal. Chem.
[
49] J. Zhi, D. Song, Z. Li, X. Lei, A. Hu, Chem. Commun. 2011, 47,
2
011, 696, 2576.
20] H. M. Emre, C. Cemil, S. M. P.Appl. Organometal. Chem. 2013,
7, 570. https://doi.org/10.1002/aoc.3034
21] M. Nasrollahzadeh, M. Atarod, S. M. Sajadi, Appl. Surf. Sci.
016, 364, 636.
10707.
[
[
[
[
[
[
[
50] A. Köllhofer, H. Plenio, Chem. Eur. J. 2003, 9, 1416.
2
51] L. R. Moore, E. C. Western, R. Craciun, J. M. Spruell, D. A.
Dixon, K. P. O'Halloran, K. H. Shaughnessy, Organometallics
2
2
008, 27, 576.
52] C. Zhou, J. Wang, L. Li, R. Wang, M. Hong, Green Chem. 2011,
3, 2100.
22] M. Nasrollahzadeh, M. Bagherzadeh, H. Karimi, J. Colloid
Interface Sci. 2016, 465, 271.
[
[
[
[
[
[
1
23] M. Atarod, M. Nasrollahzadeh, S. M. Sajadi, J. Colloid Interface
Sci. 2016, 465, 249.
53] G. Papini, M. Pellei, G. G. Lobbia, A. Burini, C. Santini, Dalton
Trans. 2009, 6985.
24] K. K. Senapati, C. Borgohain, P. Phukan, J. Mol. Catal. A 2011,
54] S. Tang, L. Kong, J. Ou, Y. Liu, X. Li, H. Zou, J. Mol. Recognit.
3
39, 24.
2006, 19, 39.
[
[
25] V. Farina, Adv. Synth. Catal. 2004, 346, 1553.
55] Z. F. Xu, G. Wen, D. Z. Kuang, F. X. Zhang, S. P. Tang,
26] A. Fihri, M. Bouhrara, B. Nekoueishahraki, J.‐M. Basset, V.
Polshettiwar, Chem. Soc. Rev. 2011, 40, 5181.
J. Environ. Sci. Health B 2013, 48, 336.
56] R. Challa, A. Ahuja, J. Ali, R. Khar, AAPS PharmSciTech 2005,
[
[
27] Y. Li, M. A. El‐Sayed, J. Phys. Chem. B 2001, 105, 8938.
6
, E329.
57] R. Sedghi, B. Heidari, M. Yassari, J. Colloid Interface Sci. 2017,
03, 47.
28] R. Narayanan, M. A. El‐Sayed, J. Am. Chem. Soc. 2004, 126,
7
194.
5
[
[
[
[
29] R. Narayanan, M. A. El‐Sayed, Langmuir 2005, 21, 2027.
30] R. Narayanan, M. A. El‐Sayed, J. Catal. 2005, 234, 348.
31] R. F. Heck, Org. React. 1982.
[
58] S. V. Bhosale, S. V. Bhosale, Mini‐Rev. Org. Chem. 2007, 4, 231.
59] M. M. Heravi, E. Hashemi, Monatsh. Chem. 2012, 143, 861.
[
[60] S. Asadi, R. Sedghi, M. M. Heravi, Catal. Lett. 2017, 147, 2045.
32] D. de Luna Martins, H. M. Alvarez, L. C. Aguiar, Tetrahedron
Lett. 2010, 51, 6814.
[61] M. M. Heravi, E. Hashemi, Y. S. Beheshtiha, S. Ahmadi, T.
Hosseinnejad, J. Mol. Catal. A 2014, 394, 74.
[
[
33] G. D. Daves Jr., A. Hallberg, Chem. Rev. 1989, 89, 1433.
[62] S. Sadjadi, M. M. Heravi, M. Malmir, Carbohydr. Polym. 2018,
1
86, 25.
[63] S. Sadjadi, M. M. Heravi, M. Raja, Carbohydr. Polym. 2018, 185,
8.
34] R. U. Islam, M. J. Witcomb, M. S. Scurrell, E. Van der Lingen,
W. Van Otterlo, K. Mallick, Catal. Sci. Technol. 2011, 1, 308.
4
[
35] J. Schwarz, V. P. Böhm, M. G. Gardiner, M. Grosche, W. A.
Herrmann, W. Hieringer, G. Raudaschl‐Sieber, Chem. Eur. J.
[64] M. Malmir, M. M. Heravi, S. Sadjadi, T. Hosseinnejad, Appl.
Organometal. Chem. 2018, 32, e4291.
2
000, 6, 1773.
[
[
36] Y. Uozumi, Y. Nakai, Org. Lett. 2002, 4, 2997.
[65] S. Sadjadi, M. M. Heravi, M. Daraie, J. Mol. Liq. 2017, 231, 98.
[66] M. M. Heravi, F. Panahi, N. Iranpoor, Org. Lett. 2018.
37] M. Mayr, M. R. Buchmeiser, Macromol. Rapid Commun. 2004,
2
5, 231.
38] J.‐H. Kim, B.‐H. Jun, J.‐W. Byun, Y.‐S. Lee, Tetrahedron Lett.
004, 45, 5827.
[
67] Y. Gu, F. Jérôme, Chem. Soc. Rev. 2013, 42, 9550. https://doi.
[
org/10.1039/C3CS60241A
2
[
68] A. Paiva, R. Craveiro, I. Aroso, M. Martins, R. L. Reis, A. R. C.
[
[
39] J.‐W. Byun, Y.‐S. Lee, Tetrahedron Lett. 2004, 45, 1837.
Duarte, ACS Sustain. Chem. Eng. 2014, 2, 1063.
40] T. Takamura, K. Endo, L. Fu, Y. Wu, K. J. Lee, T. Matsumoto,
[69] Z.‐F. Li, H. Zhang, Q. Liu, Y. Liu, L. Stanciu, J. Xie, Carbon
2014, 71, 257.
Electrochim. Acta 2007, 53, 1055.

HEIDARI ET AL.
13 of 13
[
[
[
70] Q. Zhang, K. D. O. Vigier, S. Royer, F. Jérôme, Chem. Soc. Rev.
[88] Y. Lee, M. C. Hong, H. Ahn, J. Yu, H. Rhee, J. Organometal.
Chem. 2014, 769, 80.
2
012, 41, 7108.
71] C. A. Goodman, J. B. Eagles, L. Rudahindwa, C. G. Hamaker,
[89] N. Shang, C. Feng, H. Zhang, S. Gao, R. Tang, C. Wang, Z.
S. R. Hitchcock, Synth. Commun. 2013, 43, 2155.
Wang, Catal. Commun. 2013, 40, 111.
72] S. Srivastava, V. Kumar, M. A. Ali, P. R. Solanki, A. Srivastava,
[90] N. Shang, S. Gao, X. Zhou, C. Feng, Z. Wang, C. Wang, RSC
Adv. 2014, 4, 54487.
G. Sumana, P. S. Saxena, A. G. Joshi, B. Malhotra, Nanoscale
2
013, 5, 3043.
73] S. Zhang, H. Song, P. Guo, J. Zhou, X. Chen, Carbon 2010, 48,
211.
74] W. Ruan, J. Hu, J. Qi, Y. Hou, R. Cao, X. Wei, Dent. Mater.
018, 11, 865.
[
[
[
[
[
91] L. Zhang, C. Feng, S. Gao, Z. Wang, C. Wang, Catal. Commun.
[
[
[
[
2015, 61, 21.
4
92] L. Zhang, W.‐H. Dong, N.‐Z. Shang, C. Feng, S.‐T. Gao, C.
Wang, Chin. Chem. Lett. 2016, 27, 149.
2
93] W. Dong, L. Zhang, C. Wang, C. Feng, N. Shang, S. Gao, C.
75] H. Zeng, Y. Cao, S. Xie, J. Yang, Z. Tang, X. Wang, L. Sun,
Wang, RSC Adv. 2016, 6, 37118.
Nanoscale Res. Lett. 2013, 8, 133.
94] H. A. Elazab, A. R. Siamaki, S. Moussa, B. F. Gupton, M. S. El‐
Shall, Appl. Catal. A 2015, 491, 58.
76] A. Forgas Júnior, J. Otubo, R. Magnabosco, J Aerosp. Technol.
Manag 2016, 8, 357.
95] H. A. Elazab, S. Moussa, A. R. Siamaki, B. F. Gupton, M. S. El‐
Shall, Catal. Lett. 2017, 147, 1510.
[
[
77] Q. Wang, J. Li, J. Phys. Chem. C 2007, 111, 1675.
78] Y. Xu, L. Zhang, Y. Cui, J. Appl. Polym. Sci. 2008, 110,
[96] H. A. Elazab, M. Sadek, T. T. El‐Idreesy, Adsorpt. Sci. Technol.
2018. 0263617418771777
2
996.
[
79] X. Wu, C. Lu, W. Zhang, G. Yuan, R. Xiong, X. Zhang, J. Mater.
Chem. A 2013, 1, 8645.
SUPPORTING INFORMATION
[
[
[
80] S. Paul, M. M. Islam, S. M. Islam, RSC Adv. 2015, 5, 42193.
Additional supporting information may be found online in
the Supporting Information section at the end of the article.
81] L. Yin, J. Liebscher, Chem. Rev. 2007, 107, 133.
82] T. Sakai, T. Matsunaga, Y. Yamamoto, C. Ito, R. Yoshida, S.
Suzuki, N. Sasaki, M. Shibayama, U.‐i. Chung, Macromolecules
2
008, 41, 5379.
How to cite this article: Heidari B, Heravi MM,
Nabid MR, Sedghi R, Hooshmand SE. Novel
palladium nanoparticles supported on β‐
cyclodextrin@graphene oxide as magnetically
recyclable catalyst for Suzuki cross‐coupling
reaction with two different approaches in bio‐based
solvents. Appl Organometal Chem. 2018;e4632.
https://doi.org/10.1002/aoc.4632
[
[
[
83] M. C. Hong, M. C. Choi, Y. W. Chang, Y. Lee, J. Kim, H. Rhee,
Adv. Synth. Catal. 2012, 354, 1257.
84] R. A. Sheldon, M. Wallau, I. W. Arends, U. Schuchardt, Acc.
Chem. Res. 1998, 31, 485.
85] M. B. Gawande, V. D. Bonifácio, R. Luque, P. S. Branco, R. S.
Varma, Chem. Soc. Rev. 2013, 42, 5522.
[
[
86] R. Breslow, Chem. Soc. Rev. 1991, 24, 159.
87] P. Lei, G. Meng, Y. Ling, J. An, M. Szostak, J. Org. Chem. 2017,
8
2, 6638.