The β-cyclodextrin decorated with palladium nanoparticles without pretreatment: An efficient heterogeneous catalyst for biaryls synthesis

Article abstract of DOI:10.1002/aoc.4608

β-Cyclodextrin decorated with palladium nanoparticles (PdNPs@β-CD) without pretreatment led to a suitable catalyst for the biaryls synthesis in water. A simple and straightforward method was developed for the preparation of PdNPs@β-CD as a green catalyst. The prepared catalyst was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS) measurements. It was found that PdNPs@β-CD exhibits high performance in Ullmann, Suzuki and Hiyama coupling reactions.

Full text of DOI:10.1002/aoc.4608

Received: 19 January 2018
DOI: 10.1002/aoc.4608
Revised: 31 July 2018
Accepted: 23 August 2018
F U L L P A P E R
The β‐cyclodextrin decorated with palladium nanoparticles
without pretreatment: An efficient heterogeneous catalyst
for biaryls synthesis
Afsaneh Feiz | Masood Loni | Soheila Naderi | Ayoob Bazgir
Department of Chemistry, Shahid
β‐Cyclodextrin decorated with palladium nanoparticles (PdNPs@β‐CD) with-
Beheshti University, G.C., Tehran
1983963113, Iran
out pretreatment led to a suitable catalyst for the biaryls synthesis in water.
A simple and straightforward method was developed for the preparation of
Correspondence
PdNPs@β‐CD as a green catalyst. The prepared catalyst was characterized by
Ayoob Bazgir, Department of Chemistry,
Shahid Beheshti University, G.C., Tehran
Fourier‐transform infrared spectroscopy (FT‐IR), thermogravimetric analysis
1983963113, Iran.
(TGA), X‐ray diffraction (XRD), atomic absorption spectroscopy (AAS), trans-
Email: a_bazgir@sbu.ac.ir
mission electron microscopy (TEM), and energy‐dispersive X‐ray spectroscopy
Funding information
Research Council of Shahid Beheshti
(EDS) measurements. It was found that PdNPs@β‐CD exhibits high perfor-
mance in Ullmann, Suzuki and Hiyama coupling reactions.
University
KEYWORDS
cyclodexterin, hiyama coupling, Pd‐nanoparticle, Suzuki coupling, Ullmann coupling
1 | INTRODUCTION
the heterogeneous catalysts.[5,6] In addition to the inor-
ganic supports for preparation of heterogeneous catalysts,
One of the important aspects of modern organic synthesis
is focused on designing simple, efficient, convenient,
selective and environmentally friendly catalysts in organ-
ometallic coupling reactions.[1,2] The study of simple
models of C‐C coupling reactions can evaluate the
activity, proficiency, and stability of the catalyst. These
coupling reactions, including both cross and homo
coupling of aryl halides, arylboronic acids and aryl
triethoxysilanes, are known as the most fundamental
methods for the synthesis of biaryls from a wide range
of reagents.[3] Chemists can benefit from these coupling
reactions to generate natural and complicated pharma-
ceutical molecules from simple starting materials in labo-
ratory and industry.[4]
Various metal nanoparticles‐based heterogeneous cat-
alysts have been used in ionic liquids, polymers, and
organic–inorganic fluorinated hybrid materials as well
as inorganic supports such as silica, carbon materials
and alumina for biaryls synthesis.[5] Recently, magnetic
nanoparticles are reported as an outstanding support for
some natural products such as cyclodextrins have been
used as the stabilizer and dispersing reagents in compli-
ance with green chemistry principles.[7,8]
Cyclodextrins are cyclic oligosaccharides composed of
D‐glucopyranoside units (glucose) linked by α‐1.4 glyco-
sidic bonds.[9] In particular, β‐CD with a hydrophilic
outer surface and a hydrophobic inner cavity has an
internal cavity shaped like a truncated cone of about
8 Å deep and 6.0–6.4 Å in diameter. Cyclodextrins are
the cheapest host molecules that mainly studied and are
commercially available with a wide variety of industrial
applications such as food, drug delivery, textile, and
pharmaceutical sectors.[9]
Recently, modified cyclodextrins have been used for
the heterogenization of metal nanoparticles to apply as
reusable catalysts for the organic transformations.[1,2]
Some research groups also have been reported the modi-
fication of the hydroxyl groups in cyclodextrin with
organic ligands to stabilize the metal nanoparticles.[10]
Yang and coworkers reported 1,2‐cyclohexanediamine
Appl Organometal Chem. 2018;e4608.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
1 of 8
https://doi.org/10.1002/aoc.4608

2 of 8
FEIZ ET AL.
anchored cyclodextrins as an effective catalyst for Suzuki‐
Miyaura reaction.[11] Alteration of cyclodextrin with
pyridine‐triazole complexes as bidentate ligands was also
established by Ding et al. in Suzuki‐Miyaura reaction.[11]
In spite of potential utility of aforementioned routes for
the preparation of cyclodextrin‐based catalysts, many of
these methods involve expensive reagents, multi‐step
reactions, harsh reaction conditions, long reaction times,
and use of toxic reagents for pretreatment.[11–20]
Therefore, the developing a new and efficient method
for the preparation of cyclodextrin‐based catalyst with
high catalytic activity, recyclability and simple work‐up
is of prime interest. Herein, a simple and applicable pro-
cess for the preparation of PdNPs@β‐CD as reusable
catalyst without any pretreatment for biaryls synthesis
under mild and practical conditions in water is reported.
Savings time and solvent, a non‐pretreatment method can
provide a positive environmental impact by reducing
chemical use. In addition, water is cheap and eco‐friendly
solvent and the use of water as a solvent in all coupling
reactions is one of the importance points in developing
more sustainable protocols.
addition of NaBH4 solution. After centrifuging, the
catalyst was washed with H2O, MeOH, EtOH and acetone
and dried at 60 °C.
2.3 | General procedure for Ullmann
homo‐coupling of aryl halides
A mixture of arylhalide (1 mmol), potassium carbonate
(1.5 mmol), ascorbic acid (1 mmol) and PdNPs@β‐CD
(1% mol) in distilled water (2 ml) was stirred vigorously
at 70 °C. After completion of the reaction, the solid phase
was separated by centrifuging. The aqueous phase was
then extracted with ethyl acetate (2 × 5 ml) and chloro-
form (2 × 5 ml). The organic solvents were evaporated,
and the yield was calculated after purification by prepar-
ative TLC (eluting with ethyl acetate/n‐ hexane).
2.4 | General procedure for the Suzuki
coupling of aryl halides and arylboronic
acids
A mixture of arylhalide (1 mmol), potassium carbonate
(1.5 mmol), arylboronic acid (1.1 mmol) and PdNPs@β‐
CD (1%) in distilled water (2 ml) was stirred vigorously
at 70 °C. After completion of the reaction, the mixture
was cooled to room temperature. The solid phase was
separated by centrifuging, and the aqueous phase was
then extracted with ethyl acetate (2 × 5 mL) and chloro-
form (2 × 5 ml). The biaryl product was purified using
preparative TLC after evaporation of the organic solvents,
and the yield was calculated based on aryl halide.
2 | EXPERIMENTAL
2.1 | Material and measurements
Melting points were determined on a melting point appa-
ratus and are uncorrected. IR spectra were taken with a
Bomem FT‐IR MB spectrometer. The NMR spectra were
recorded on a BRUKERDRX‐300AVANCE spectrometer.
Diffraction data were collected on a STOE STADI P with
scintillation detector, secondary monochromator and
Cu‐Ka1 radiation (λ =1.5406 Å). EDS characterizations
of PdNPs@β‐CD were performed using an electron
microscopy Philips XL‐30 ESEM. Transmission electron
microscopy characterization of PdNPs@β‐CD was per-
formed using a transmission microscope Philips CM‐30
with an accelerating voltage of 150 kV. The concentration
of PdNPs was estimated using Shimadzu AA‐680 flame
atomic absorption spectrophotometer. All chemicals were
purchased from Merck or Aldrich and were used without
further purification.
2.5 | General procedure for the Hiyama
cross‐coupling reaction
A mixture of aryl halide (1 mmol), triethoxy (phenyl)
silane (1.3 mmol), NaOH (4 mmol), PdNPs@β‐CD
(1% mol) and distilled water (2 ml) was stirred vigorously
for an appropriative time that indicated in Table 4. After
completion of the reaction, the solid phase was separated
by centrifuging and subsequently the aqueous phase was
extracted with ethyl acetate (2 × 5 mL) and chloroform
(2 × 5 ml). The product was isolated after evaporating
the organic solvents, and the yield was calculated based
on aryl halide.
2.2 | Preparation of PdNPs@β‐CD
β‐Cyclodextrin (1 mmol) was dissolved in hot water to
obtain a colorless solution. A solution of Pd (OAc)2
(0.8 mmol) in warm CH3CN was added at room temper-
ature to the β‐Cyclodextrin solution with a vigorously
mixing. After 1 hr, a freshly prepared solution of NaBH4
(0.5 M) in water was added dropwise to the solution.
The black nanoparticles appeared immediately with the
3 | RESULTS AND DISCUSSION
The PdNPs@β‐CD catalyst was prepared according to the
procedure shown in Figure 1. First, a solution of Pd
(OAc)2 in a minimum amount of hot acetonitrile was
added to a solution of β‐CD in distilled water. The β‐CD

FEIZ ET AL.
3 of 8
FIGURE 1 Schematic representations of PdNPs@β‐CD catalyst
have a number of hydroxyl groups (secondary OH
groups) on the outside of the cyclic cavity that can pro-
vide plenty of coordination sites to chelate metal ions
and form covalent bonds.[21,22] Therefore, Pd (II) ions
are coordinated by the secondary OH groups of cyclodex-
trin and make distribution of the Pd (II) iones on the
cyclodextrin support to form Pd (II)@β‐CD. Conse-
quently, palladium nanoparticles were obtained after
addition of a freshly prepared solution of NaBH4 to Pd
(II)@β‐CD. It is noticeable that the heterogeneous
catalyst just obtained in presence of reducing agent. The
NaBH4 reduce Pd (II)@β‐CD solution to PdNPs@β‐CD
as a black powder.
be seen in the FT‐IR spectrum of β‐CD the appearance
of the strong bands at 3397, 1030 and 1170 cm−1 was
assigned to O‐H, C–OH and C–O–C stretching bands of
β‐CD. In the FT‐IR spectrum of PdNPs@β‐CD, the
appearance of the characteristic band of β‐CD in 1600
region confirms the presence of β‐CD clearly in the final
catalyst.[23] Also, the band shift from 1647 cm−1(in
β‐CD) to 1636 cm−1 in PdNPs@β‐CD revealed the coordi-
nation of Pd NPs to β‐CD.[24]
The EDS of of PdNPs@β‐CD is shown in Figure 3.
The presence of Pd indicates that the Pd nanoparticles
are loaded in the final catalyst. The EDS analysis also
reveals the presence of the elemental composition of
β‐cyclodexterin (C and O) in prepared catalyst. Atomic
absorption spectroscopy (AAS) was used by dissolving
palladium content of PdNPs@β‐CD in aqua regia to
The prepared PdNPs@β‐CD was characterized by
FT‐IR, EDS, XRD, and TEM. The FT‐IR spectrum of
β‐CD and PdNPs@β‐CD are shown in Figure 2. As can
FIGURE 2 The FT‐IRspectrum of β‐CD and PdNPs@β‐CD

4 of 8
FEIZ ET AL.
FIGURE 5 XRD pattern of PdNPs@β‐CD
3.1 | Ullmann homo‐coupling reaction
catalyzed by PdNPs@β‐CD in water
FIGURE
PdNPs@β‐CD
3
Energy dispersive X‐ray spectrum (EDS) of
The catalytic activity of PdNPs@β‐CD was evaluated in
the Ullmann homo‐coupling of aryl halides. The homo‐
coupling reaction of iodobenzene in water at 70 °C was
selected as a model reaction. To optimize the reaction
conditions, different experiments were accomplished by
various bases and reductants in the presence of different
amount of catalyst. The reaction was carried out with
0.5, 1 and 2 mol% of catalyst in the presence of glucose
as reductant (Entries 1–3) and K2CO3 as a base for
24 hr. As can be seen from Table 1, the 1 mol% of catalyst
was sufficient to push this reaction forward (Entry 2).
Then, the different reducing agents such as ascorbic acid,
sodium formate, and glucose were tested. The results in
Table 1 showed that ascorbic acid is the best choice
(Entry 4). Furthermore, a series of bases including
Cs2CO3, K2CO3, and KOtBu were screened, we found
K2CO3 led to the best yield. We also performed several
experiments at room temperature, 60 °C, 70 °C, and
80 °C in H2O using 1 mol% of catalyst for 24 hr
(Table 1, entries 4, 8 and 9). The most suitable reaction
temperature was 70 °C (Table 1, entry 4).
calculate the palladium content in PdNPs@β‐CD sample
(3.75 mmol.g−1).
The transmission electron microscopy (TEM) was
used to study the morphology of the PdNPs@β‐CD.
The TEM image of PdNPs@β‐CD showed the appropri-
ate distribution of near spherical palladium nanoparti-
cles with no significant aggregation of Pd nanoparticles.
The average size of palladium nanoparticles was
estimated to be around12–15 nm (Figure 4) which is
larger than the cavity of β‐CD. This confirms that the
PdNPs are distributed on the outside of the cyclic cavity
of β‐CD.
The synthesized PdNPs@β‐CD crystallinity was
examined by XRD analysis. As revealed in Figure 5, three
distinct and broad reflections positioned at 2θ =38.6°,
44.3° and 65.9° were related to the palladium nanoparti-
cles for (111), (200) and (220) planes, respectively. These
three reflections represent the face centered cubic (fcc)
structure of PdNPs. On the basis of the half width of the
(111) reflection, the PdNPs@β‐CD average crystallite size
(~17 nm) was calculated by using the Debye‐Scherer
equation.[18]
Various aryl iodides and bromides were screened
under optimized conditions in the reductive Ullmann
homo‐coupling reaction (Table 2) to determine the scope
FIGURE 4 TEM images of PdNPs@β‐CD

FEIZ ET AL.
5 of 8
TABLE 1 Reaction optimization conditions for reductive
Ullmann homo‐coupling of iodobenzenea
3.2 | Suzuki coupling reaction catalyzed
by PdNPs@β‐CD in water
The Suzuki coupling reaction of arylhalides and
arylboronic acids was chosen as the second coupling reac-
tion for the biaryls synthesis under optimized reaction
conditions in water (Table 3). The ability of the catalyst
in the Suzuki coupling reaction was clearly proved when
a different arylboronic acids and aryl iodides and bro-
mides reacted well and gave the desired products in good
yields after 2 h. The Suzuki coupling reaction of phenyl
chloride and phenylboronic acid led to the product in
67% yield (Table 3, entry 6).
Catalyst
Entry Base
(mol %) T (Co) Reductant
Yield (%)b
1
K2CO3 0.5
70
70
70
70
70
70
70
80
60
50
r.t
70
glucose
70
76
78
90
2
K2CO3
K2CO3
K2CO3
K2CO3
KOtBu
Cs2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
1
2
1
1
1
1
1
1
1
1
1
glucose
3
glucose
4
ascorbic acid
5
sodium formate 77
6
ascorbic acid
ascorbic acid
ascorbic acid
ascorbic acid
ascorbic acid
ascorbic acid
‐
65
85
7
3.3 | Hiyama cross‐coupling reaction
catalyzed by PdNPs@β‐CD in water
8
91
9
63
The application of the PdNPs@β‐CD catalyst further
expanded in Hiyama cross‐coupling reaction of triethoxy
(phenyl) silane and aryl halides in water. The Hiyama
reaction of iodobenzene and triethoxy (phenyl) silane at
the optimized reaction conditions was tested, and the cor-
responding product was obtained in 78% yield (Table 4,
entry 1). It was found that increasing amounts of the cat-
alyst to 2 mol% did not improve the yield (Table 4, entry
2). A review of the literature revealed that NaOH is a
good choice as the base.[25] Consequently, we checked
the reaction in water using NaOH in the presence of
1 mol% of catalyst and biphenyl as a product was
obtained in 92% yield (Table 4, entry 3). The catalyst
showed a good reactivity in the Hiyama reaction of differ-
ent aryl halides with triethoxy (phenyl) silane (Table 4,
Entries 3–9). The Hiyama reaction of arylchlorides pro-
duced the target products in good yields (entry 9–12).
10
11
12
46
<20
<20
aIodobenzene (1 mmol), base (1.5 mmol), reductant (1 mmol), H2O (1 ml).
Reaction time = 24 h.
bIsolated yield,
TABLE 2 Synthesis of biaryls via Ullmann homo‐coupling of aryl
halidesa
Entry
R
X
Yield(%)b
1
2
3
4
5
6
7
8
H
I
90
96
40
95
85
80
82
80
4‐Me
2‐Me
4‐COMe
H
I
TABLE 3 The Suzuki reaction of aryboronic acids and aryl
halidesa
I
I
Br
Br
Br
Br
4‐NO2
3‐OMe
4‐Me
Entry
R
X
R′
Yield(%)
aAryl halide (1 mmol), K2CO3 (1.5 mmol), ascorbic acid (1 mmol) and Cat.
(1 mol%).
bIsolated yield
1
2
3
4
5
6
H
I
H
93
84
85
86
78
67
4‐OMe
4‐Me
H
I
4‐OMe
H
I
Br
Br
Cl
H
4‐NO2
H
4‐Me
H
of the reaction. The catalyst showed good efficiency
for the differently substituted aryl iodides and aryl
bromides in water. Under the same reaction conditions,
the homo‐coupling of arylchlorides failed to provide the
target product.
aAryl halide (1 mmol), arylboronic acid (1.1 mmol),K2CO3 (2 mmol) and Cat.
(1 mol%).
bIsolated yield.

6 of 8
FEIZ ET AL.
TABLE 4 The Hiyama reaction of triethoxy (phenyl) silane with
aryl halidesa
reusability of the catalyst was also investigated in Suzuki,
Ullmann, and Hiyama reactions. The catalyst could be
reused at least six times successively without significant
loss of activity (Figure 6). All results confirmed the reac-
tion occurs mainly via a heterogeneous pathway.
Table 5, compares the efficiency and capability of
PdNPs@β‐CD catalyst with other reported β‐CD‐based
catalysts in the Suzuki coupling reaction. The most
similar study to the present work is the use of Pd (II)
@β‐CD as homogeneous catalyst for Suzuki coupling
reaction (Table 5, entry 1). The coupling mechanism of
Pd(+2/+4) was recognized by mercury drop test for this
study. As a consequence of homogeneous nature of Pd
(II), the catalyst efficiency fell down 26% after 4 runs.[8]
But, the present heterogeneous catalyst with coupling
mechanism of Pd(0/+2) showed low loss in activity
after six runs. Moreover, the catalysis separation in the
homogeneous Pd (II)@β‐CD catalyst is more difficult
than present heterogeneous system. The Table 5 shows
that all the methods based CD catalysts have good
efficiency in coupling reactions, but some of these
methods suffer from one or more of the drawbacks such
as using an organic solvent (entry 4), higher temperatures
(entries 2, 4 and 7) and require longer reaction times
(entries 2, 3, 4 and 6) to afforded reasonable yields. The
most of the previous reports are based on the modifica-
tion of the hydroxyl groups of cyclodextrin with organic
ligands such as thiol ligand, hexagonal boron‐nitride
ligand, N,N,O tridentate ligand, pyridinium ligand and
pyridine‐azole based ligand (entries 4–8). The present
catalytic system without any pretreatment offered high
catalytic activity under mild and reasonable reaction
conditions for the biaryls synthesis.
Entry
R
X
Time (h)
Yield (%)b
1c
2d
3
H
I
6
6
6
6
6
6
7
7
8
8
8
8
78
80
92
90
89
93
90
85
87
85
80
87
H
I
H
I
4
4‐Me
4‐NH2
4‐COMe
H
I
5
I
6
I
7
Br
Br
Cl
Cl
Cl
Cl
8
Naphthyl
H
9
10
11
12
4‐NH2
Naphthyl
4‐NO2
aAryl halide (1 mmol), triethoxy (phenyl)silane(1.3 mmol), KOH (4 mmol)
and Cat. (1 mol%).
bIsolated yield.
cK2CO3 as base, 1 mol % catalyst.
dK2CO3 as base, 2 mol % catalyst.
After evaluation of the catalytic performance in differ-
ent coupling reactions, we examined the heterogeneous
nature of the catalyst. First, we performed a mercury
poisoning test by entering an excess amount of Hg in
the Suzuki reaction of phenylboronic acid and phenyl
iodide. The reaction yield fell down in the presence of
mercury due to the amalgamation with PdNPs. The
results confirm us the heterogeneous nature of the
catalyst, moreover it can be concluded that Suzuki
reaction proceeded via Pd(0)/Pd(+2) mechanism.[26,27]
In the next step, to assess the palladium leaching from
catalyst during the reaction, we performed the hot
filtration test for Suzuki reaction of phenyl iodide and
phenylboronic acid. The reaction was stopped after
~50% of the reaction was completed. The hot filtrates
were then transferred to another flask containing base
and H2O at 70 °C. Upon further heating of the catalyst‐
free solution for 4 h, no considerable progress (~ 6% by
GC analysis) was observed. Moreover, using AAS, the
same reaction solution at the midpoint of completion
indicated that no significant quantities of palladium were
lost to the reaction liquors during the process. Also, the
palladium content of reused PdNPs@β‐CD catalyst after
six runs was determined by AAS which showed no signif-
icant leaching of palladium during the reactions. The
FIGURE 6 The reusability of the catalyst in the Suzuki reaction
of phenyl iodide and phenylboronic acidaa Suzuki reaction: phenyl
iodide (1 mmol), phenylboronic acid (1.1 mmol), K2CO3 (2 mmol)
and Cat. (1 mol%).b Ullmann reaction: phenyl iodide (1 mmol),
K2CO3 (1.5 mmol), ascorbic acid (1 mmol) and Cat. (1% mol).
cHiyama reaction: Phenyl iodide (1 mmol), triethoxy (phenyl) silane
(1.3 mmol), NaOH (4 mmol) and Cat. (1 mol%)

FEIZ ET AL.
7 of 8
TABLE 5 Comparison of efficiency of various heterogeneous catalysts for Suzuki coupling reactiona
Entry
Catalyst
Solvent
Time (h)
T (°C)
Yield (%)
Ref.
[8]
1
2
3
4
5
6
7
8
9
Pd (II)@β‐CD
H2O
1
4
4
4
1
6
2
2
2
80
90
91
71
85
88
81
86
91
98
86
b
[28]
[16]
[18]
[29]
[30]
[31]
[12]
Pd (II)@β‐CD@Fe3O4
H2O
Pd(0)@CD@Graphenec
Pd (II)@SH‐βCDd
H2O
90
CH3CN/H2O
H2O
100
70
Pd (II)@H‐BN@CDe
Pd (II)@DAP@β‐CDf
Pd (II)@Pyr‐β‐CDg
Pd (II)@Py‐Az@β‐CDh
PdNPs@β‐CD
H2O
80
H2O
90
H2O
80
H2O
70
This work
aSuzuki reaction of phenylboronic acid with phenyl bromide.
bPalladium decorated β‐cylodexterin modified magnetic nanoparticle (Fe3O4).
cPalladium nanoparticles decorated β‐cylodexterin modified graphene nanoparticles.
dPalladium modified thiol functionalized β‐cylodexterin.
ePalladium anchored hexagonal boron‐nitride modified cyclodexterin.
fPalladium coordinated N,N,O tridentate Ligand modified cyclodexterin.
gPalladium coordinated pyridinium modified β‐cylodexterin.
hPalladium capped pyridine‐azole modified β‐cylodexterin.
[3] L. Yin, J. Liebscher, Chem. Rev. 2007, 107, 133.
4 | CONCLUSION
[4] A. J. J. Lennox, G. C. Lloyd‐Jones, Chem. Soc. Rev. 2014, 43, 412.
[5] I. Maluenda, O. Navarro, Molecules 2015, 20, 7528.
To sum up, PdNPs@β‐CD substrate was prepared through
an absolutely simple, readily available starting materials
and convenient procedure without using any toxic
reagents. The catalyst showed well to excellent reactivity
under green conditions for the synthesis of symmetrical
and unsymmetrical biaryls in homo and cross coupling
reaction of Ullmann, Suzuki, and Hiyama. Notably,
β‐cyclodextrin was used without further modification for
the synthesis of the catalyst. The negligible leaching of
palladium from catalyst was proved by AAs, and the
catalyst was recovered by simple filtration and reused
for several cycles without a significant loss of activity.
[6] M. Tukhani, F. Panahi, A. K. Nezhad, ACS Sustainable Chem.
Eng. 2018, 6, 1456.
[7] P. Taladriz‐Blanco, P. Herves, J. Pérez‐Juste, Top. Catal. 2013,
56, 1154.
[8] B. Kaboudin, H. Salemi, R. Mostafalu, F. Kazemi, T.
Yokomatsu, J. Organomet. Chem. 2016, 818, 195.
[9] J. W. Steed, J. L. Atwood, Supramolecular Chemistry, 2nd ed.,
Wiley 2009.
[10] W. Zhao, Q. Zhong, J. Inclusion Phenom. Macrocyclic Chem.
2012, 72, 1.
[11] G. Zhang, Y. Luan, X. Han, Y. Wang, X. Wen, C. Ding, J. Gao,
Green Chem. 2013, 15, 2081.
ACKNOWLEDGEMENT
[12] J. Liu, J. Julio Alvarez, W. Ong, E. Román, A. E. Kaifer, Lang-
muir 2001, 17, 6762.
We gratefully acknowledge the financial support from the
Research Council of Shahid Beheshti University.
[13] J. Alvarez, J. Liu, E. Roman, A. E. Kaifer, Chem. Commun.
2000, 1151.
[14] R. Imran Khan, K. Pitchumani, Green Chem. 2016, 18, 5518.
ORCID
[15] S. Hong, M. Liu, Y. Shuai, Z. Wang, L. Shi, W. Deng,
J. Inclusion Phenom. Macrocyclic Chem. 2014, 80, 443.
Ayoob Bazgir http://orcid.org/0000-0002-9655-6606
[16] C. Putta, V. Sharavath, S. Sarkar, S. Ghosh, RSC Adv. 2015, 5,
6652.
REFERENCES
[17] L. Strimbu, J. Liu, A. E. Kaifer, Langmuir 2003, 19, 483.
[18] U. Holzwarth, N. Gibson, Nat. Nanotechnol. 2011, 6, 534.
[1] M. Sollogoub, Synlett 2013, 24, 2629.
[2] S. Noel, B. Leger, A. Ponchel, K. Philippot, A. Denicourt‐
Nowicki, A. Roucoux, E. Monfiler, Catal. Today 2014, 235, 20.
[19] M. T. Rojas, R. Koniger, J. F. Stoddart, A. E. Kaifer, J. Am,
Chem. Soc. 1995, 117, 336.

8 of 8
FEIZ ET AL.
[20] X. Zhao, X. Liu, M. Lu, Appl. Organomet. Chem. 2014, 28, 635.
[30] A. Das, D. K. Mishra, B. Sinha, J. Coord. Chem. 2017, 70, 3035.
[31] R. I. Khan, K. Pitchumani, Green Chem. 2016, 18, 5518.
[21] Y. Chao, Z. Y. Jin, X. M. Xu, H. N. Zhuang, W. Y. Shen, Food
Chem. 2008, 109, 264.
[22] D. Prochowicz, A. Kornowicz, J. Lewinsk, Chem. Rev. 2017,
117, 13461.
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.
[23] N. V. Roik, L. A. Belyakova, P.C.S.S. 2011, 12, 168.
[24] J. Wang, Y. Zong, X. Wang, Y. Hu, G. Yue, Y. Pan, Green Chem.
2016, 18, 967.
[25] E. Alacid, C. Najera, J. Org. Chem. 2008, 73, 2315.
[26] J. C. Holder, A. N. Marziale, M. Gatti, B. Mao, B. M. Stoltz,
Chem. A Eur. J. 2013, 19, 74.
How to cite this article: Feiz A, Loni M,
Naderi S, Bazgir A. The β‐cyclodextrin decorated
with palladium nanoparticles without
pretreatment: An efficient heterogeneous catalyst
for biaryls synthesis. Appl Organometal Chem.
2018;e4608. https://doi.org/10.1002/aoc.4608
[27] J. C. Holder, L. Zou, A. N. Marziale, P. Liu, Y. Lan, M. Gatti, K.
Kikushima, K. N. Houk, B. M. Stoltz, J. Am. Chem. Soc. 2013,
135, 14996.
[28] H. Salemi, B. Kaboudin, F. Kazemi, T. Yokomatsu, RSC Adv.
2016, 6, 52656.
[29] S. Rui, C. Xu, L. Weijian, L. Pengfei, Z. Yong, Chem. Res. Chin.
Univ. 2017, 33, 811.