Water soluble starch stabilized palladium nanoparticle: Efficient catalyst for Miyaura-Suzuki coupling reaction

Article abstract of DOI:10.1002/cjoc.201090117

The fabricated water soluble starch stabilized palladium nanoparticle promoted Miyaura-Suzuki coupling reaction with high catalytic activity and selectivity and in excellent yields, which include recovery and re-use of this catalyst at least three times.

Full text of DOI:10.1002/cjoc.201090117

FULL PAPER
Water Soluble Starch Stabilized Palladium Nanoparticle: Effi-
cient Catalyst for Miyaura-Suzuki Coupling Reaction
Liu, Shiyong*(刘诗咏)
Zhou, Qizhong*(周其忠)
Jiang, Huajiang(蒋华江)
Department of Chemistry, Taizhou University, Taizhou, Zhejiang 317000, China
The fabricated water soluble starch stabilized palladium nanoparticle promoted Miyaura-Suzuki coupling reac-
tion with high catalytic activity and selectivity and in excellent yields, which include recovery and re-use of this
catalyst at least three times.
Keywords soluble starch, nanoparticle, palladium, Miyaura-Suzuki coupling reaction, aryl bromide
Introduction
geneous nanosize palladium catalysts with a ligand of
phosphine with a TPPh moiety, in situ generated pal-
1
8
Palladium-catalyzed cross-coupling reactions such
as Heck reaction, Kumada reaction, Stille reaction, Ne-
gishi reaction, Miyaura-Suzuki reaction and Sonoga-
shira reaction are the most important processes to con-
struct C—C bonds in modern organic synthesis.
ladium nanoparticles in PEG-400 under aerobic condi-
19
tions and Pd on surface-modified NiFe
2
O
4
nanoparti-
20
cles highly efficiently promoted coupling reaction of
aryl chlorides with arylboronic acids in good to excel-
lent yields.
Miyaura-Suzuki reaction with high stability, broad
functional group tolerance, as well as low toxicity asso-
ciated with boron compounds as one of the most
well-known reactions was widely used in the selective
fabrication of symmetric and unsymmetric biaryl com-
Water is cheap, environmentally benign and green.
In this decade, many reactions have been carried out in
21
aqueous media using Pd or nano-Pd.
Starch is eatable and nontoxic, which was widely
used in food, drug carrier, medicine and industry.
1
2
pounds, the synthesis of herbicides, pharmaceuticals,
22
Wallen et al. prepared starched silver nanoparticle
3
4
natural products, bioactive molecules, microelectrode
from soluble starch as stabilizer, β-D glucose as reduc-
ing reagent and AgNO .
3
5
arrays and engineering materials such as conducting
polymers, molecular wires and liquid crystalline materi-
In this paper, we reported the synthesis and catalytic
activities for the Miyaura-Suzuki coupling reaction in
DMF-water and the recovery and reusability of water
soluble starch stabilized palladium nanoparticle catalyst
with low catalyst loadings.
6
als.
Most recently, palladium nanoparticles attracted
much attention in Miyaura-Suzuki reation. Air-stable
and highly active dendritic phosphine oxide-stabilized
palladium nanoparticles, sulphonated “click” den-
drimer-stabilized palladium nanoparticles, palladium
7
8
Experimental
nanoparticles stabilized by star-shaped heavily fluorous
9
compounds, palladium nanoparticles on polysaccha-
Preparation of water soluble starch stabilized palla-
dium nanoparticle
1
0
ride-derived mesoporous materials, palladium nano-
clusters supported on propylurea-modified siliceous
mesocellular foam, palladium nanoparticles supported
Na
PdCl
starch solution (0.3 wt%) and sodium ascorbate aqueous
solution (0.1 mol/L) were prepared. Na PdCl (0.1
2
4
PdCl (0.1 mol/L in water) was prepared from
11
(1 g) and NaCl (0.68 g) in water. Water soluble
1
2
3
2
on alumina-based oxides as heterogeneous catalysts,1
Pd nanoparticles on carbon nanotube microparticles,
2
4
Pd nanoparticles immobilized on pH-responsive and
chelating nanospheres and in situ-generated palladium
mol/L, 2 mL) was added into a stirred water solution of
starch (0.3 wt%, 20 mL). The mixture turned amaranth.
After addition, the mixture was further stirred for 5 min.
Sodium ascorbate aqueous solution was slowly added
into the above stirred solution till the mixture turned
sandy beige and even dark. Then the addition was
stopped and water soluble starch stabilized palladium
nanoparticle was obtained.
1
4
1
5
nanoparticles free of ligand highly efficiently cata-
lyzed aryl halides (X＝Br, I) with aryl and alkylboronic
acids in good to excellent yields. Palladium nanoparti-
cles supported on polyaniline nanofibers as
a
1
6
semi-heterogeneous catalyst, in situ generated palla-
dium nanoparticles from PEG-400/Pd(OAc)
1
7
2
,
homo-
*
E-mail: chelsy@zju.edu.cn; qizhongchou@yahoo.com
Received September 3, 2009; revised February 5, 2010; accepted March 29, 2010.
Project supported by the National Natural Science Foundation of China (No. 20476092) and the Taizhou University (No. 09ZD12).
Chin. J. Chem. 2010, 28, 589— 593
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
589

Liu et al.
FULL PAPER
General procedure for the water soluble starch sta-
bilized palladium nanoparticle catalyzed Suzuki
coupling reaction
TEM measurements
Morphology and microstructure were investigated by
TEM (Philips CM-20 SuperTwin operating at 200 kV
and providing 0.25 nm resolution). Analyses of TEM
images were made with the Image J program. Speci-
mens for TEM were prepared by dispersing a solution
sample and placing a droplet of the suspension onto a
copper microscope grid covered with perforated carbon.
To a mixture of a solution of the above catalyst (1
mL) and NaOAc (0.l5 g, 2 mmol) in DMF (5 mL) at 80
℃
, bromobenzene (1 mmol) and phenylboronic acid
1.2 mmol) were added. The mixture was stirred at 80
(
℃
for 1.5 h. After the mixture cooled, the reaction mix-
ture was extracted with diethyl ether for three times.
The combined ether solution was detected with GC to
measure conversions. The extracted residue was used
Results and discussion
for the next cycle.
The water soluble starch stabilized palladium nano-
particle was prepared from water soluble starch as stabi-
1
3
a: H NMR (CDCl
3
, 400 MHz, TMS) δ: 7.60 (d,
J＝7.5 Hz, 4H), 7.44 (t, J＝7.2 Hz, 4H), 7.35 (t, J＝7.2
2 4
lizer, Na PdCl as Pd source and NaVc (sodium vitamin
＋
Hz, 2H); LRMS (EI, 20 eV) m/z (%): 154 (M , 100).
C) as reductant.
1
3
b: H NMR (CDCl
3
, 400 MHz, TMS) δ: 7.73 (d,
It is well known that the Suzuki reaction requires a
base to promote the reaction. Our initial investigation
started with the cross coupling reaction of bromoben-
zene and phenylboronic acid as a model reaction. The
reaction was carried out in the presence of 0.1 mol%
water soluble starch stabilized palladium nanoparticle in
DMF/water (5∶1, V∶V) at 80 ℃. Several bases were
tested (Table 1). All bases gave good to excellent yields.
Of all the bases tested, NaOAc affords the highest yields
for the Suzuki reaction.
J＝8.5 Hz, 1H), 7.69 (d, J＝8.5 Hz, 2H), 7.65 (d, J＝
8
2
.5 Hz, 2H), 7.52 (t, J＝7.0 Hz, 2H), 7.44 (t, J＝6.5 Hz,
＋
H); LRMS (EI, 20 eV) m/z (%): 188 (M , 100).
1
3
c: H NMR (CDCl
3
, 400 MHz, TMS) δ: 7.20—7.24
(
m, 2H), 7.29—7.35 (m, 4H), 7.45—7.51 (m, 4H), 7.54
1
3
3
(s, 4H); C NMR (100 MHz, CDCl ) δ: 127.7, 129.4,
1
2
27.9, 135.4, 136.5, 128.4; LRMS (EI, 20 eV) m/z (%):
＋
30 (M ,100).
1
3
d: H NMR (CDCl
3
, 400 MHz, TMS) δ: 8.32 (d,
J＝9.0 Hz, 2H), 7.75 (d, J＝9.0 Hz, 2H), 7.64 (d, J＝
a
7
1
.0 Hz, 2H), 7.51 (t, J＝7.5 Hz, 2H), 7.46 (t, J＝7.2 Hz,
Table 1 Effect of various bases on the Suzuki reaction
＋
H); LRMS (EI, 20 eV) m/z (%): 199 (M , 100).
Entry
Base
NaOAc
NaOH
KF
Time/h
1.5
Diphenyl/%
1
3
e: H NMR (CDCl
3
, 400 MHz, TMS) δ: 7.20—7.24
1
2
3
6
7
96
73
85
88
83
(
(
1
3
m, 3H), 7.29—7.35 (m, 6H), 7.45—7.51 (m, 6H), 7.66
1
3
s, 3H); C NMR (100 MHz, CDCl
3
) δ: 136.5, 137.5,
1.5
25.2, 127.9, 129.3, 127.7; LRMS (EI, 20 eV) m/z (%):
1.5
＋
06 (M , 100).
1
K
3
PO
4
1.5
3
f: H NMR (CDCl
3
, 400 MHz, TMS) δ: 7.58 (d,
K CO
2
1.5
J＝7.5 Hz, 2H), 7.49 (d, J＝8.0 Hz, 2H), 7.43 (t, J＝7.5
3
a
Hz, 2H), 7.32 (t, J＝7.3 Hz, 1H), 7.25 (d, J＝7.5 Hz,
Bromobenzene (1 mmol), phenylboronic acid (1.2 mmol); water
soluble starch stabilized Pd nanoparticles as catalyst, 0.1 mol%
Pd; DMF/H O (5∶1, V∶V, 6 mL) mixture as solvent, 80 ℃.
＋
2
H), 2.39 (s, 3H); LRMS (EI, 20 eV) m/z (%): 168 (M ,
1
00).
2
1
3g: H NMR (CDCl
3
, 400 MHz, TMS) δ: 7.54 (m,
4
6
H), 7.42 (t, J＝7.7 Hz, 2H), 7.28 (t, J＝14.8 Hz, 1H),
With the optimized conditions in hand, reactions of
various arylhalides with phenylboronic acid gave excel-
lent yields except 4-nitrophenylchloride (Table 2). As
can be seen, the Suzuki cross coupling reaction showed
a high selectivity between iodine atom and chlorine
atom (Entry 2, Table 2). The catalyst is less active to-
ward the aromatic chlorides than the aromatic bromides
and aromatic iodides. From Table 2, we know phenyl-
bromide (or phenyliodide) with electron withdrawing
groups needed less time, while those with electron do-
nating groups needed longer time.
.98 (d, J＝4.3 Hz, 2H), 3.86 (s, 3H); LRMS (EI, 20 eV)
＋
m/z (%): 184 (M , 100).
1
3
3
h: H NMR (CDCl , 400 MHz, TMS) δ: 7.53 (d,
J＝8.0 Hz, 2H), 7.36—7.39 (m, 4H), 7.15—7.18 (m,
2
6
H), 7.26 (t, J＝7.8 Hz, 1H), 6.76 (d, J＝8.0 Hz, 1H),
.75 (t, J＝8.5 Hz, 2H), 3.70 (s, 2H); LRMS (EI, 20 eV)
＋
m/z (%): 169 (M , 100).
1
3
i: H NMR (CDCl
3
, 400 MHz, TMS) δ: 7.22—7.32
(
2
1
d, J＝8.0 Hz, 5H), 7.48 (s, 2H), 6.79 (d, J＝8.5 Hz,
1
3
3
H), 5.0 (s, 1H); C NMR (100 MHz, CDCl ) δ: 116.4,
27.7, 127.9, 129.3, 136.5, 157.4.
Next, we examined the reusability of the Pd
nano-catalyst in Suzuki reaction. A series of 6 consecu-
tive runs were carried out in DMF/water (5∶1, V∶V, 6
mL) at 80 ℃ in the presence of the starch stabilized Pd
nanoparticle catalyst. At the end of the each reaction,
the collected water soluble starch stabilized Pd catalyst
was reused for a new batch. As shown in Table 3, Cycle
1
3
j: H NMR (CDCl
3
, 400 MHz, TMS) δ: 7.22 (1H),
7
7
.29—7.34 (m, 4H), 7.45—7.49 (m, 2H), 7.38 (s, 1H),
1
3
3
.63 (s, 1H), 7.67 (s, 2H); C NMR (100 MHz, CDCl )
δ: 136.7, 134.1, 127.9, 134.4, 136.5, 128.3,125.1, 129.3,
＋
127.2, 126.8; LRMS (EI, 20 eV) m/z (%): 204 (M ,
1
00).
1
to cycle 3 gave excellent yields. The yield does not
5
90
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Chin. J. Chem. 2010, 28, 589— 593

Water Soluble Starch Stabilized Palladium Nanoparticle
Table 2 Suzuki reaction of various arylhalides with phenylboronic acid
a
b
Entry
1
X
I
R
Time/h
0.5
Product
Yield /%
4-H
97
95
90
3
a
2
3
I
I
4-Cl
4-Ph
0.5
1
3
b
3c
4
5
Br
Br
4-NO
4-Br
2
1
1
97
87
3
d
3c
6
Br
3,5-Br
1.5
91
3e
7
8
Br
Br
4-Ph
4-H
1.5
1.5
3c
3a
86
96
9
Br
Br
Br
Br
4-CH
3
1.5
1.5
3
92
88
85
88
3
f
10
11
12
4-OMe
3
g
4-NH
2
3
h
4-OH
3
3i
1
3
4
Br
Cl
3
86
3
j
c
1
4-NO2
20
3d
49
a
0
2
Arylhalides (1.0 mmol), PhB(OH) (1.2 mmol), NaOAc (2 mmol), water soluble starch stabilized Pd nanoparticles as catalyst, 0.1
b
c
mol% Pd; DMF/H O (5∶1, V/V, 6 mL) as solvent, 80 ℃, air atmosphere. Isolated yields. Reaction carried out at 150 ℃ for 20 h.
2
Chin. J. Chem. 2010, 28, 589— 593
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www.cjc.wiley-vch.de
591

Liu et al.
FULL PAPER
decrease much before the third cycle. After cycle 3, the
yield decreased sharply, which was attributable to the
enlarged size of the nanoparticle resulting from con-
tinuing heat, which decreased the activity of the cata-
lyst.
ger after each cycle. Thus, the catalyst lost some cata-
lytic activity. After 3 cycles, the catalytic activity de-
creased sharply. The larger size and sharper contrast
(Figure 1d) suggest that the crystallization of the Pd
nanoparticle got higher with the increased recycle times.
Table 3 Reusability of the starch stabilized palladium nano-
particle for Suzuki reaction of phenylbromide and phenylboronic
acid
Conclusion
In conclusion, the fabricated water soluble starch
stabilized palladium nanoparticle catalyst free of ligand
showed excellent catalytic activity and selectivity for
the Suzuki cross coupling reactions. The catalyst is an
efficient catalyst to promote the Suzuki coupling reac-
tion for arylbromide/aryliodide and phenylboronic acid
in excellent yields. Such high catalytic activities are
supposed to result from the small size, narrow size dis-
tribution, and high surface area of the Pd nanoparticles.
The catalyst could be separated and recovered from re-
action mixtures easily by simple extraction. Surely, con-
tinuing heating enlarged the size of the nanoparticle,
which decreased the activity of the catalyst. The major
additional point is the recoverability of the catalyst with
an efficient re-use only at least three times and without
obvious loss of its catalytic activity to a large extent.
The catalyst would be the ideal homogeneous catalyst
for the Suzuki cross coupling reactions. The application
of the catalyst in other reactions such as hydrogenation
at room temperature as template reaction which may
enhance the activity and reusability of the catalyst is on
the progress.
Recycle number
Yield/%
1
2
3
4
5
6
96 91 87 55 43 20
The transmission electron microscopy (TEM) im-
ages of the starch stabilized palladium nanoparticle,
freshly prepared, after the first cycle, after the second
cycle and after the third cycle are shown in Figure 1.
As shown in Figure 1, the size of the freshly pre-
pared nanopalladium was 5—7 nm. The size of the
nanopalladium after the first cycle was 10—15 nm. The
size of the nanopalladium after the second cycle was 20
—
25 nm. The size of the nanopalladium after the third
cycle was 50—70 nm. In principle, the catalytic activity
of nano-catalyst was determined by the size of nanopar-
ticles. The smaller the size of nanoparticle is, the more
effective the catalytic activity is. After every reaction,
part of the starch molecules went away from the surface
of palladium nanoparticles. Meanwhile, palladium
nanoparticle aggregated and the degree of crystallization
improved. Then, the size of nanopalladium became lar-
Figure 1 TEM images of Pd nanoparticles freshly prepared (a), after 1st cycle (b), 2nd cycle (c) and 3rd cycle (d).
5
92
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Water Soluble Starch Stabilized Palladium Nanoparticle
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Chin. J. Chem. 2010, 28, 589— 593
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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