Pd(II)-β-cyclodextrin complex: Synthesis, characterization and efficient nanocatalyst for the selective Suzuki-Miyaura coupling reaction in water

Article abstract of DOI:10.1016/j.jorganchem.2016.06.007

Herein we report the preparation, characterization and the catalytic ability of novel Pd(II)-β-cyclodextrin complex as an efficient nanocatalytic system for the Suzuki-Miyaura carbon-carbon (C-C) coupling reaction in water. The presented novel Pd(II)-β-cyclodextrin complex catalyst was characterized by TGA, FT-IR, XRD, NMR and atomic absorption analysis. Also, by using the Pd(II)-β-CD complex as a homogeneous catalyst, we have developed an efficient protocol for suzuki-Miyaura coupling reaction of aryl boronic acids with aryl halides in neat water with high turnover frequencies (TOFs) for the synthesis of unsymmetrical biaryls. The catalyst can be recycled and reused multiple times to catalyze the coupling reaction.

Full text of DOI:10.1016/j.jorganchem.2016.06.007

Accepted Manuscript
Pd(II)-β-cyclodextrin complex: Synthesis, characterization and efficient nanocatalyst
for the selective Suzuki-Miyaura coupling reaction in water
Babak Kaboudin, Hadi Salemi, Ramin Mostafalu, Foad Kazemi, Tsutomu Yokomatsu
PII:
S0022-328X(16)30257-1
10.1016/j.jorganchem.2016.06.007
JOM 19524
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 16 January 2016
Revised Date: 30 April 2016
Accepted Date: 5 June 2016
Please cite this article as: B. Kaboudin, H. Salemi, R. Mostafalu, F. Kazemi, T. Yokomatsu, Pd(II)-
β-cyclodextrin complex: Synthesis, characterization and efficient nanocatalyst for the selective
Suzuki-Miyaura coupling reaction in water, Journal of Organometallic Chemistry (2016), doi: 10.1016/
j.jorganchem.2016.06.007.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Pd-β−CD (0.001 mol%)
Ar1 B(OH)2
X=I, Br
Ar1 Ar2
+
Ar2
X
K2CO3 (1.5 equiv)
H2O, reflux
Pd-β−CD:

ACCEPTED MANUSCRIPT
Pd(II)-β-Cyclodextrin Complex: Synthesis, Characterization
and Efficient Nanocatalyst for the Selective Suzuki-Miyaura
Coupling Reaction in Water
Babak Kaboudin
*a Hadi Salemi,a Ramin Mostafalu,a Foad Kazemia and
,
Tsutomu Yokomatsub
a
Department of Chemistry, Institute for Advanced Studies in Basic Sciences,Gava zang, Zanjan,
Iran. Fax: 98 241 4214949; Tel: 98 241 4153220; E-mail: kaboudin@iasbs.ac.ir
School of Pharmacy, Tokyo University of Pharmacy and Life Sciences,14321-1 Horinouchi,
b
Hachioji, Tokyo 192-0392, Japan
Abstract. Herein we report the preparation, characterization and the catalytic ability of novel
Pd(II)-β-cyclodextrin complex as an efficient nanocatalytic system for the Suzuki–Miyaura
carbon-carbon (C-C) coupling reaction in water. The presented novel Pd(II)-β-cyclodextrin
complex catalyst was characterized by TGA, FT-IR, XRD, NMR and atomic absorption
analysis. Also, by using the Pd(II)-β-CD complex as a homogeneous catalyst, we have
developed an efficient protocol for suzuki-Miyaura coupling reaction of aryl boronic acids
with aryl halides in neat water with high turnover frequencies (TOFs) for the synthesis of
unsymmetrical biaryls. The catalyst can be recycled and reused multiple times to catalyze the
coupling reaction.
Keywords: β-Cyclodextrin; Boronic acids; Suzuki–Miyaura coupling; Pd(II)-β-cyclodextrin
complex
Introduction
During the past decades, water soluble catalysts have been current interest to developing
novel catalysts for greener chemical processes and synthetic methods [1-9]. Water soluble
catalysts with active metal species and ligands having suitable hydrophilic groups are widely
used in organic reactions, due to environmental and economical consideration [10].
Palladium-catalysed Suzuki-Miyaura hetero-coupling reactions have been used as the most
fundamental reactions for the construction of biaryl componds [11-13]. The Suzuki-Miyaura
hetero-coupling reactions are practically popular in the pharmaceutical and chemical
industries, due to its benefits of functional group compatibility, excellent yield of products,
and mild reaction conditions [14-17]. However, the Suzuki-Miyaura hetero-coupling reactions
usually carried out in organic solvents in the presence of phosphine ligands without catalyst
recycle, which limit their industrial application in terms of cost performance and organic
wastes processing. Hence, the use of organic solvents and phosphine ligands is better to be
avoided in palladium-catalysed Suzuki-Miyaura hetero-coupling reactions [18].
Cyclodextrins (CDs) are well-known macrocyclic oligosaccharide structures composed of
6, 7 or 8 units of D-glucopyranoses, namely α-CD, β-CD and γ-CD, respectively [19]. CDs
have a rigid cyclic structure with hydrophilic external rims and a hydrophobic cavity that
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shows excellent performances in aqueous organic reactions [20]. Moreover, Cyclodextrins as
supramolecular molecules have ability to prepare inclusion complex with metal ions, which
make them efficient water soluble catalysts with high stability in water, specially, for
palladium-catalysed Suzuki-Miyaura hetero-coupling reactions [21, 22].
Recently, Ding et. al. have reported preparation of a novel palladium(II) complex with a
functionalized β-CD tethered to a pyridyltriazole moiety and its application for the Suzuki-
Miyaura coupling reaction in water [23]. More recently, an inclusion complex between a
hydrophilic β-CD and a hydrophobic palladium(II)-dipyrazole complex bearing an adamantyl
(Ad) molecular as a recognition moiety has been reported by Hor et. al. for Suzuki-Miyaura
coupling reaction [24]. Although the use of β-CD and functionalized β-CD as a ligand in the
presence of Pd(II) was previously described in Suzuki-Miyaura coupling reaction, catalyst
recycling was not possible and high catalyst loading was used under reaction condition
[25]. In our recently efforts on developing nanocatalysts applicable to greener chemical
processes, we have found that the inclusion complex of Cu(II) and β-CD (Cu(II)-β-CD
complex) is an efficient nanocatalyst for the homocoupling reaction of arylboronic acids. A
feature of this complex is that the modified β-CDs are not required for its preparation [26-28].
On the basis of our experience with assemblig metal complexes of β-CD, we have now
designed a novel inclusion complex of Pd(II) with β-CD (Pd(II)-β-CD complex). Herein, we
now disclose the preparation and characterization of a novel Pd(II)-β-CD complex and its
application as an efficient catalyst for Suzuki-Miyaura hetero-coupling reaction in water.
Experimental
General methods
All compounds and solvents were purchased from commercial suppliers. Melting points were
taken on a Buchi 510 apparatu. NMR spectra were obtained on a Bruker Avance 400 NMR
Spectrometer (1H NMR: 400 MHz, 13C NMR: 100 MHz). Gas chromatography was
performed on a Varian CP 3800 chromatograph. Thermogravimetric analysis was conducted
from room temperature to 800 °C in an oxygen flow using a NETZSCH STA 409 PC/PG
instrument. FT-IR spectra were recorded using a Bruker Vector 22 instrument after mixing
the samples with KBr. The palladium content in the complex was determined using Varian
spectra 110 atomic absorption spectrometry. Analytical TLC was carried out with Merck
plates precoated with silica gel 60 F254 (0.25 mm thick). Column chromatography was
performed either with FLUKA Silica gel 60 (70-230 mesh) in common glass columns.
Preparation of Pd(II)-β-CD
Solution of β-cyclodextrin (1 mmol, 1.135 g) in 0.5 M NaOH (50 ml) was prepared in a 250
ml Becker containing with stirring. To this clear solution, Pd(OAc)2 (3 mmol, 0.673 g) was
added. After solving the Pd(OAc)2 a light yellow solution was obtained and stirred in room
temperature for 12 h. Then ethanol (about 500 ml) was added to this solution until the light
yellow suspension was appeared. Precipitated Pd(II)-β-CD complex was filtrated and washed
with ethanol and dried in room temperature (1.30 g Pd(II)-β-CD). The 2.3:1 ratio of Pd to
cyclodextrin was determined by atomic absorption analysis that reveals a binuclear Pd(II)-β-
CD complex. m.p: 241°C decomposed.
General procedure for the hetero-coupling of aryl boronic acids with aryl halides
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To a mixture of Pd(II)-β-CD (0.001 mol%, based on palladium, 0.23 mL from a solution of 1
mg in 100 mL water, see Table 2 for amount of catalyst) in 2 mL water was added aryl halide
(0.2 mmol), arylboronic acid (0.24 mmol), and K2CO3 (0.3 mmol). The resulting mixture was
stirred at reflux for 1-12 h (Table 2). After cooling, the product was extracted with n-hexane
(2x3 mL) and dried over Na2SO4. The product was purified by flash chromatography and
1
13
characterized with H and CNMR (in CDCl3 and DMSO solvents) to afford biaryls 3a-s in
56-100 % yields. All products are known and most of them are commercially available (see
supporting information).
Catalyst recycling
After a model Suzuki-Miyaura reaction of 4-bromoanisole and phenylboronic acid in water,
the product was isolated by two-phasic system (see general procedure). The clear aqueous
solution was transferred to a clean flask, and measured amounts of fresh substrate were added
with stirring at reflux. After the required time had elapsed and after cooling the, the product
was extracted with n-hexane (2x3 mL) and dried over Na2SO4.
Results and discussion
The inclusion complex of Pd(II) with the β-CD (Pd(II)-β-CD complex) has never been
prepared and studied. Pd(II)-β-CD complex was prepared with the same method for the
preparation of Cu(II)-β-CD complex described by Matsui with a slight modification[29, 30].
β-CD was dissloved in 0.5 M NaOH with stirring and Pd(OAc)2 was added to the solution.
The supernatant became yellow after 1 h at room temperature. The solution was stirred for
additional 12 h and ethanol was added to the yellow solution until the light yellow suspension
was formed. The solid was filtrated and washed with ethanol to give Pd(II)-β-CD complex
(Scheme 1).
1) NaOH (0.5 M)
Pd(OAc)2
+ β-CD
Pd(II)-β-CD
2) EtOH
a light yellow solid
Scheme 1. The preparation of Pd(II)-β-CD complex
The structure of the prepared Pd(II)-β-CD complex were characterized by TGA, XRD, NMR,
and FT-IR analyses, which confirmed the successful preparation of the Pd(II)-β-CD complex.
Fig.1 shows the TGA spectra of Pd(OAC)2, a 1:1 mixture of Pd(OAC)2 and β-cyclodextrin,
and Pd(II)-β-CD complex, respectively. As shown in Fig. 1, the termogravimetric analysis
curve of the Pd(II)-β-CD complex shows a weight loss of 9.99% below 120 oC due to the loss
of the adsorbed water in the sample. Also about 50.24% weight loss in the range of 120-
320oC is attributed to the thermal decomposition of Pd(II)-β-CD complex. The TGA curve of
the complex (Fig. 1c) is completely different with TGA curve of a mixture of Pd(OAC)2 and
β-cyclodextrin (Fig. 1b). TGA of the complex shows that the thermal stability of β-CD is
lower than the complex. Similar results were obtained for the complex of Fe(III)-β-CD
complex reported by Rossi [31].
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Figure 1. TGA curve of a) Pd(OAC)2 b) a mixture of Pd(OAC)2 and β-cyclodextrin c) Pd(II)-β-CD
complex
The 2.3:1 ratio of Pd to cyclodextrin was determined by atomic absorption analysis that
reveals a binuclear Pd(II)-β-CD complex. The TGA curve and atomic absorption analysis
confirmed the successful formation of Pd(II)-β-CD complex.
Fig. 2 shows the FT-IR spectra of β-cyclodextrin and Pd(II)-β-CD complex in the 400-4000
cm-1 wave number range. It shows that the broad band 3000-3900 cm-1 is due to the hydroxyl
stretching vibration adsorption band in the β-cyclodextrin, which narrowed after being
bonded with Pd. The spectrum of Pd(II)-β-CD complex shows the characteristic vibrations
4

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peaks of β-cyclodextrin at the 800-1620 cm-1 range. The peak at 1030 cm-1 corresponds to the
anti-symmetric C-O-C vibrations. The intense peak at 1627 cm-1 may be assigned to the
deformation vibrations of water molecules trapped into the Pd(II)-β-CD complex [32].
Figure 2. FT-IR spectrum of (a) β-cyclodextrin and (b) Pd(II)-β-CD
1
The complex formation of the Pd(II) with β-cyclodextrin was also estimated by the H NMR
1
analysis of Pd(II)-β-CD complex. As shown in Fig. 3, the H NMR (400 MHz) of the
complex shows significant signal broadening as a consequence of the presence of Pd(II)
bonded to β-cyclodextrin. The line broadening is particularly for the multiplets signals
corresponding to the OH groups bonded to carbons 2, 3 and 6 at 5.70 and 4.45 ppm. The
NMR spectrum is similar to reported by Rossi et al. for Fe(III)-β-CD complex [31].
5

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b
a
Figure 3. 1H NMR spectrum (DMSO, 400 MHz) of (a) β-cyclodextrin and (b) Pd(II)-β-CD
The crystal structure of the Pd(II)-β-CD complex was also studied by XRD analysis (Fig. 4).
The XRD pattern of the Pd(II)-β-CD complex indicates that the prepared Pd(II)-β-CD
complex is pure without any Pd(0) in the structure. This reveals that the β-cyclodextrin, as a
stabilizing ligand, plays a major role in stabilization of the Pd(II) ions in the reduction process
to Pd(0) in aqueous media.
Fig. 4. XRD pattern of the Pd(II)-β-CD
The catalytic behavior of the Pd(II)-β-CD complex was studied for the synthesis of
unsymmetrical biaryls via Suzuki-Miyaura coupling reaction of aryl boronic acids with aryl
halides in water. Initially, the heterocoupling of phenylboronic acid 1a with p-bromoanisole
2a in water was chosen as the model reaction. When the reaction was carried out using
Pd(II)-β-CD complex (0.005 mol%, based on palladium) for 1 h at reflux in water, biaryl 3a
was obtained in a 77% isolated yield in the presence of sodium carbonate as base (1.5 equiv)
(Table 1).
By screening of different bases, including K2CO3, Cs2CO3 and K3PO4 (Entries 1-4), we found
that K2CO3 was the best one using Pd(II)-β-CD complex (0.005 mol%) for 1 h at reflux in
water (Entry 2). The coupling reaction yield decreases to 11% with decreasing the reaction
temperature to ambient temperature (Entries 5-7). It should be noted that homo-coupling
product was obtained as side product when the reaction was carried out using Pd(II)-β-CD
(0.005 mol%,) for 24 h at ambient temperature (Entry 8). The results showed that the homo-
coupling product was not observed when the reaction carried out at reflux temperature in
6

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water. As could be seen in Table 1, the best result was obtained with a 0.001 mol% of Pd(II)-
β-CD complex as the catalyst in refluxing water for 1 h (Entry 9)
Table 1. Hetero-coupling of phenylboronic acid 1a with p-bromoanisole 2a in water using Pd(II)-β-CD
complex as a catalyst
Pd(II)-β−CD
base (1.5 equiv)
H2O, 1 h
B(OH)2
MeO
Br
+
MeO
3a
1a
2a
(1.2 equiv)
Entry
Catalyst (mol%)
Base
T (°C)
Conversion
%a 3a
1
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.001
0.0001
0.001
0.005
CDd
Na2CO3
K2CO3
K3PO4
Cs2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
-
reflux
reflux
reflux
reflux
80
77
96
65
71
70
31
11
54b
96
70
5
2
3
4
5
6
60
7
rt
8
rt
9
reflux
reflux
reflux
reflux
reflux
10
11
12c
13
K2CO3
73
K2CO3
N.R
a ) Conversions determined by GC based on 2a, b) Reaction time:24 h, a
40% homo-coupling side product (biphenyl) was obtained, c) Mercury
poisoning test (400 equiv of Hg), d) 1 equiv cyclodextrin
The blank experiment showed that without Pd(II)-β-CD complex, the reaction could not
occur. It should be noted that the mercury drop test and poison experiment was examined to
further study of the catalytically properties of Pd(II)-β-CD complex. Mercury is known to
form an amalgam with Pd(0). The Suzuki– Miyaura reaction between 1a and 2a in water
using Pd(II)-β-CD complex as a catalyst and K2CO3 as a base in the presence of a drop of
Hg(0), biaryl 3a was obtained in a 73% isolated yield (entry 12). These results showed that
the Pd(0) was not formed in the reaction mixture.
Under the above optimized conditions (Entry 9), the scope of the Suzuki-Miyaura hetero-
coupling reaction of various arylboronic acids with aryl halides catalyzed by the Pd(II)-β-CD
complex in water at reflux was investigated.
As shown in Table 2. The hetero-coupling of boronic acid derivatives with various aryl
iodides gave corresponding biaryls in good to excellent yields (entries 1-12). Arylboronic
acids bearing both electron-donating and -withdrawing groups gave the corresponding biaryl
in excellent yield (entries 4-6). Whereas the 3,5-difluorophenylboronic acid provided the
corresponding biaryl 3i in a 93% yield (entry 9), 2,6-dimethylphenylboronic acid with high
steric congestion around the boronic acid functional group failed to give the desired biaryl
(entry 10). Moreover, hetero-coupling reaction of 1-naphthyl boronic acid substrate with high
7

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degree of hydrophobicity and potential steric hinderance was achived in excellent yield in
water (entry 11). The hetero-coupling of aryl boronic acids with various aryl bromides also
gave corresponding unsymmetrical biaryls in good to excellent yields (entries 13-26). For the
coupling reaction of 1-bromo naphthalene with phenylboronic acid, the catalytic activity of
Pd(II)-β-CD complex at 0.001 mol% loading was not satifactory and only 6% of coupling
product was obtained by increasing the amount of catalyst to 0.01 mol% (entry 27). The
hetero-coupling of phenylboronic acid with 4-chlorobenzene gave corresponding biaryl 3k in
56% yield (entry 29) at 0.05 mol% loading of Pd(II)-β-CD catalyst. The reaction failed to
give the desired biaryl in the presence of 0.001 mol% of catalyst (entry 28).
Table 2. Pd(II)-β-CD-catalyzed hetero-coupling of arylboronic acid 1 with aryl halide 2
Pd(II)-β−CD (0.001 mol%)
Ar1 B(OH)2
Ar1 Ar2
+
Ar2 Br
K2CO3 (1.5 equiv)
H2O, reflux
3
2
1
(1.2 equiv)
Time
(h)
Conversiona
(%)
Entry
Ar1 (1)
Ar2 (2)
X
mol (%)
Product (3)
TOF,b h-1
1
2
3
4
5
6
7
8
Ph
Ph
Ph
Ph
I
I
I
I
I
I
I
I
I
0.001
1
1
1
2
2
2
4
3
2
24
3
4
1
1
2
1
3
3
3
1
4
4
4
4
4
3
12
8
4
96
92
80
98
99
96000
92000
80000
49000
49500
8700
3700
5600
46500
-
3300
4450
100000
96000
45000
100000
27666
17000
19400
100000
20250
3650
4250
3750
19750
30333
100
3a
3b
3c
3d
3b
3e
3f
3g
3h
-
3i
3j
3k
3b
3a
3l
3m
3d
3d
3n
3o
3b
3p
3q
3r
3s
3i
4-MeOC6H4
4-ClC6H4
0.001
0.001
0.001
0.001
0.005
0.005
0.005
0.001
0.05
4-MeC6H4
Ph
Ph
Ph
Ph
Ph
Ph
4-MeOC6H4
3-O2NC6H4
2-Naphthyl
2-Benzofuranyl
3,5-F2C6H3
87
74c
84c
93
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
2,6-dimethylC6H3 Ph
I
I
I
N.R
99
89
100
96
91
100
83
51
1-Naphthyl
2-MeC6H4
Ph
Ph
Ph
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeOC6H4
4- MeOC6H4
4- MeOC6H4
2-Naphthyl
2-benzofuranyl
3,5-F2C6H3
Ph
Ph
Ph
0.01
0.005
0.001
0.001
0.001
0.001
0.001
0.001
0.005
0.001
0.001
0.005
0.005
0.005
0.001
0.001
0.01
4-OHCC6H4
4- MeOC6H4
Ph
4-CHO-C6H4
4- MeOC6H4
Ph
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Ph
97
4-CHO-C6H4
4- MeOC6H4
Ph
4- MeOC6H4
4- MeOC6H4
4- MeOC6H4
5-Pyrimidine
1-Naphthyl
4- OHCC6H4
4- OHCC6H4
100
81c
73
85c
75d
79c
91
6
-
56
Ph
Ph
Ph
0.001
0.05
-
3k
3k
280
Conversions determined by GC based on aryl halide, b) TOF was defined as mol product mol-1 h-1, c) Isolated yield, d)
1HNMR yield
a)
Pd
From the green chemistry point of view, the attention is focused mainly on the recycling
8

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of metal catalysts, especially in Pd catalysts. We verified that after work up of Suzuki-
Miyaura coupling reaction of 4-bromoanisole and phenylboronic acid as a model reaction,
aqueous phase have ability to catalyze the reaction of freshly added substrates yet.
The catalytic activity did not decrease considerably after four catalytic cycles (Table 3).
The reaction yield dropped to ca. 79% at the second run and was 70% by the 4th recycling
step. It should be noted that catalyst decomposition to form palladium black is not
observed in the reaction and β-cyclodextrin was found to be effective satabilize the
catalyst against decomposition and made recycling feasible.
Table 3. Reusability test of Pd(II)-β-CD (0.01 mol%) catalysed hetero-coupling of 4-
bromoanisole (0.2 mmol) and phenylboronic acid (0.24 mmol) in the presence of K2CO3 (0.3
mmol) in water
Conversion
(%)
1st run
2nd run
3rd run
4th run
Average
Yield
(%)
Product
96
79
74
70
80
3b
Acknowledgements
The authors gratefully acknowledge the support of the Institute for Advanced Studies in Basic
Sciences (IASBS).
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ACCEPTED MANUSCRIPT
Highlights
• Preparation of novel water soluble Pd(II)-β-cyclodextrin complex without any ligand.
• Suzuki-Miyaura catalytic coupling reaction with high TOF (105 mol product mol-1
h )
-1
Pd
•
The catalytic behavior of the Pd(II)-β-cyclodextrin complex in coupling reaction for a large scope
of aryl boronic acids and aryl halides in water
•
Reusability of Pd(II)-β-cyclodextrin homogeneous catalyst in Suzuki-Miyaura coupling reactions
for several times.