Palladium supported on aminopropyl-functionalized polymethylsiloxane microspheres: Simple and effective catalyst for the Suzuki-Miyaura C-C coupling

Article abstract of DOI:10.1016/j.molcata.2015.07.002

Abstract A palladium catalyst, obtained in the reaction of PdCl₂(MeCN)₂ with microspheric aminopropyl polymethylsiloxane, was used in the Suzuki-Miyaura cross-coupling of various aryl bromides with phenylboronic acids. Catalytic reactions, performed at 80°C in a 2-propanol/water mixture, led to high yields of non-symmetric biphenyls. In recycling experiments, excellent results (up to 100%) were obtained in ten subsequent runs. Efficient separation of the catalyst from organic products was achieved by simple filtration due to the properties of microspheres.

Full text of DOI:10.1016/j.molcata.2015.07.002

Journal of Molecular Catalysis A: Chemical 407 (2015) 230–235
Contents lists available at ScienceDirect
Journal of Molecular Catalysis A: Chemical
journal homepage: www.elsevier.com/locate/molcata
Palladium supported on aminopropyl-functionalized
polymethylsiloxane microspheres: Simple and effective catalyst for
the Suzuki–Miyaura C–C coupling
a
b
b
a,∗
Wojciech Zawartka , Piotr Po s´ piech , Marek Cypryk , Anna M. Trzeciak
a
Faculty of Chemistry University of Wrocław, 14 F. Joliot-Curie, 50-383 Wrocław, Poland
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Engineering of Polymer Materials, 112 Sienkiewicza, 90-363 Łód ´z , Poland
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 28 May 2015
Received in revised form 22 June 2015
Accepted 2 July 2015
Available online 9 July 2015
A palladium catalyst, obtained in the reaction of PdCl (MeCN) with microspheric aminopropyl
2
2
polymethylsiloxane, was used in the Suzuki–Miyaura cross-coupling of various aryl bromides with
◦
phenylboronic acids. Catalytic reactions, performed at 80 C in a 2-propanol/water mixture, led to high
yields of non-symmetric biphenyls. In recycling experiments, excellent results (up to 100%) were obtained
in ten subsequent runs. Efficient separation of the catalyst from organic products was achieved by simple
filtration due to the properties of microspheres.
Keywords:
Palladium
©
2015 Elsevier B.V. All rights reserved.
Polymethylsiloxane
Microspheres
Suzuki–Miyaura
1
. Introduction
used in the Heck reaction [45,46] and the Suzuki–Miyaura coupling
47,48].
Although palladium catalysts supported on siloxanes function-
[
Heterogenized palladium-based catalytic systems, widely used
for the carbon–carbon bond formation reactions, have been attract-
ing more and more attention because of increasing environmental
requirements [1–7].
alized with imidazole and triazole groups have been successfully
recycled [47,48], the separation step has been rather complicated in
these systems due to the very small diameter of the beads formed by
polysiloxane. Centrifugation has not been efficient and very care-
ful filtration through a thick filter allowed to solve the problem of
catalyst recovery.
Therefore, we decided to examine the catalytic activity
of palladium supported on aminopropyl-functionalized poly-
methoxysiloxane in the form of microspheres [49,50]. It was
expected that palladium supported on polymethoxysiloxane
microspheres would be active in the Suzuki–Miyaura reaction and,
in addition, its recyclability would be improved. It is also worth
noting that polymethoxysiloxanes are chemically and thermally
resistant non-toxic materials.
In the context of green chemistry, the advantage of immobi-
lization consists in the efficient separation of the catalyst and its
recycling in the next several runs to increase its productivity. As a
result, a lower cost of the catalytic process and the minimization
of the metal content in the final organic product can be achieved.
This aspect is especially very important in pharmaceutical appli-
cations, where the final product is predominantly in contact with
living organisms.
Palladium complexes bonded to differently functional-
ized polymers have been used in catalysis [8–21], including
the Suzuki–Miyaura reaction [22–30]. Pd(0) stabilized on
polyvinylpyrrolidone [31–37], polyvinylpyridine [38,39] or
other polymers has been widely applied [40–43]. However, very
few reports have presented on the application of functionalized
silicone polymers [44] as catalyst supports. At the same time,
polysiloxane-supported palladium has recently been successfully
This article aims to report on the application of NH2-
modified siloxane polymers as supports for palladium catalysts in
Suzuki–Miyaura carbon–carbon coupling reactions.
2. Results and discussion
2.1. Structural studies
∗ Corresponding author. Fax: +48 71 3282348.
E-mail address: anna.trzeciak@chem.uni.wroc.pl (A.M. Trzeciak).
Coordination of palladium to aminopropyl polymethoxysilox-
ane resulted in a change of the composition and a decrease in N,
http://dx.doi.org/10.1016/j.molcata.2015.07.002
1
381-1169/© 2015 Elsevier B.V. All rights reserved.

W. Zawartka et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 230–235
231
Fig. 1. Representation of the catalyst structure.
C, and H amounts in comparison with the free support, which is
2.2. Suzuki–Miyaura cross-coupling reactions
one of the proofs of palladium connection to the carrier surface.
The Pd/N ratio, calculated from the N and Pd contents (measured
by ICP), indicated that there were 10% of amino groups coordinated
to the palladium ion. The most probable structure of [Pd], contain-
The Suzuki–Miyaura reaction of aryl bromides with substituted
phenylboronic acids was selected as a model catalytic reaction for
testing a new palladium catalyst (Fig. 8).
ing palladium bonded to two NH groups and two chloride ions, is
shown in Fig. 1.
Due to the heterogeneous nature of the catalyst, it was required
to carry out the reaction at a higher temperature such as 80 C to
2
◦
Because of the insolubility of the polymer in organic solvents,
C and Si NMR spectra were measured in the solid state.
obtain optimum conversion in a satisfactory time and to prolong
the reaction time to 6 h.
13
29
The SEM analysis shows that palladium is evenly distributed
For testing reactions, two different bases (KOH and KHCO3)
were chosen. Potassium hydroxide is a strong base, while potas-
sium hydrocarbonate is considered a medium or even a weak base.
However, both are known for their outstanding performance in
palladium-catalyzed coupling reactions. As a solvent, a mixture of
water and 2-propanol was used, regarded to be safe to use and
environmentally friendly.
on the surface of the spheres, and its amount does not differ for
samples before and after the catalytic reaction (Table 1). Negligi-
ble differences in the amounts of palladium between samples can
show the lack of leaching of the metal from the support during the
reaction. This demonstrates the very strong and stable bond of pal-
ladium to the NH2 groups. During the reaction Pd(II) is reduced
to Pd(0) nanoparticles. Functional groups (NH ) of the polymer
Test reactions were performed for different aryl halides with
phenylboronic acid, in order to select the most reactive substrates
and then to check their coupling with other substituted boronic
acids. The obtained conversions of aryl halides are presented in
Table 2.
Generally, both the bases turned out to be good. The reaction
yields were comparable, but in most of the reactions KOH was
slightly better and made it possible to achieve higher halide con-
versions, up to 100%.
2
play a role of stabilizers preventing agglomeration of nanoparti-
cles. The observed interactions can be described as coordination to
the palladium metallic surface due to the Lewis base properties of
the polymer NH2 groups, similarly as it was discussed in [36]. In
this form it can be consistently observed very strong metal support
interaction, which prevents the elution of the Pd and the unwanted
entry into the reaction products.
The SEM picture of the catalyst sample analyzed after the Suzuki
reaction performed with KOH as the base showed some structural
changes (Figs. 4 and 5) indicating the partial decomposition of the
support.
Reactions with different halides and phenylboronic acid showed
conversions from 0% for 2-bromoacetophenone to 100% for bro-
mobenzene and 3-bromobenzaldehyde. The highest conversions,
The reaction mixture under these conditions is very basic, which
leads to the destruction of the polymer in the fragments where
there are no functional groups. In particular, the fragment where
there are free H or OMe groups can be attacked (Figs. 2–5). It
appears that the amino group linked to the palladium remains
intact, and this was also confirmed by the solid state NMR anal-
ysis of the support before and after the reaction, which showed
that the chemical shifts of the representative carbons and silicones
did not change much. TEM microscopy evidenced the presence
of palladium nanoparticles bonded to the organic matrix, most
probably by functional groups extended from the surface of the
spheres (Figs. 6 and 7). Thus, during the catalytic reaction, Pd(II)
was reduced to Pd(0) nanoparticles, similarly as it was observed for
other catalysts supported on polysiloxane polymers (Fig. 1) [47,48].
up to 100%, were obtained for halides with OH, NH , NO , or CN
2 2
substituents in the phenyl ring. Substrates with only methyl or
methoxy groups were a little less reactive. Conversions for them
ranged from 42% for 4-bromotoluene to 66% for 2-bromotoluene
and 2-bromo-3-xylene.
For further studies, 4-bromobenzaldehyde was selected as a
representative halide. Reactions with substituted boronic acids
showed conversions from 30% for 2-isopropyl-6-methoxyphenyl
boronic acid to 100% for 4-tert-butylphenyl and naphthalene
boronic acid derivatives. In this case, there is no effect of the specific
substituent on the reaction yield. Generally, yields were very good
to excellent. It should also be noted that during all the performed
reactions only traces (up to 3%) of homo-coupling of the boronic
acid product were observed. Quantity of biphenyl was determined
by GC-FID, and estimated from the ratio of the signals areas of the
main and the side products.
Table 1
Average palladium content on the sample surface measured with EDS.
2.3. Reuse and recycling of the catalyst
Sample
palladium content in the
sample
The most important feature of heterogenized catalysts is their
(
weight% +/− 0.01)
ability to be reused, so-called recycling. During the research, such
a test was also carried out. The catalyst was easily reused due to
the fact that it floated on the surface of the water phase of a bi-
phasic catalytic mixture. At the end of the catalytic reaction, the
Before reaction
After reaction with KHCO3 as a base
After reaction with KOH as a base
0.25
0.23
0.26

2
32
W. Zawartka et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 230–235
Figs. 2 and 3. Catalyst surface (SEM) before (left) and after (right) one reaction with KHCO3 as the base.
Figs. 4 and 5. Catalyst surface (SEM) after one and ten reactions with KOH as the base.
Figs. 6 and 7. Catalyst surface (TEM mag. 180 K, 930 K) after one reaction with KOH as the base.
Fig. 8. Suzuki–Miyaura C–C coupling reaction scheme.

W. Zawartka et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 230–235
233
Fig. 9. Catalyst reuse.
organic phase was separated, and a new portion of the substrates
was added. The test made it possible to carry out ten consecutive
reaction cycles without a significant reduction of the activity of the
catalyst (Fig. 9).
The second series of recycling was performed using the catalyst
separated from the reaction mixture and used for the coupling of
showed great activity in this experiment, making it possible to
obtain a 100% conversion of the substrates.
It should also be underlined that the recovery of the catalyst
from the reaction mixture is very simple and requires only filtration
on a medium dense filter.
Under the operating reaction conditions, a two-phase system
is formed (Fig. 10). One phase is composed of water-soluble
components, i.e., the base and the boronic by-products of the
reaction. The other phase contains the organic reactants and the
reaction products. The solid catalyst is at the interface between
4
-bromobenzaldehyde with phenylboronic acid. The catalyst also
Table 2
Suzuki-Miyaura coupling reaction of aryl bromides [2] with arylboronic acids.
Entry
R
R’
KOH
KHCO3
Conv.[%]
Conv.[%]
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
4-NH2
4-OH
2-Me
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
98
100
61
53
64
66
0
100
100
100
94
99
85
66
42
46
54
0
4-Me
2-OMe
2,5-Me
2-Ac
H
94
58
99
99
99
86
61
36
30
42
72
67
77
97
99
78
99
99
100
3-CHO
4-CHO
3-NO2
4-NO2
2,5-Me, 4-NO2
2-CN
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
96
100
100
99
33
40
76
89
90
95
98
99
100
100
100
4-CN
4-CHO
4-CHO
4-CHO
4-CHO
4-CHO
4-CHO
4-CHO
4-CHO
4-CHO
4-CHO
4-CHO
2-iPr, 6-OMe
4-Vinyl
H, Pinacol ester
4-COOH
4-CHO
4-Ac
3,5-OMe
4-Boronic acid
4-Me, 1-Nap
1-Nap
4-tBu
Reaction conditions: aryl halide (1 mmol), arylboronic acid (1.2 mmol), [Pd] (2 mol%,
0
8
.02 mmol Pd), base (2 mmol), solvent (2-propanol/water- 1:1, 5 mL), temperature
◦
0
C, time 6 h.
Fig. 10. Two-phase reaction system.

2
34
W. Zawartka et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 230–235
given temperature for 6 h and, after that time, left for several min-
utes to cool down. Next, the organic products were separated by
extraction with 10 mL of diethyl ether. The extracts (10 mL) were
GC-FID analyzed with dodecane (0.050 mL) as an internal standard
to determine the conversion of aryl bromide. The products of the
reaction were determined by GC–MS.
3.3. Suzuki–Miyaura kinetic studies reaction procedure
Suzuki–Miyaura reactions were performed in a Schlenk tube.
Weighed amounts of the solid reactants: phenylboronic acids
3.3 mmol), base (4.0 mmol), catalyst (20.00 mg), aryl bromide (1
(
Fig. 11. Kinetic studies of the Suzuki–Miyaura reaction.
mmol), and 12 mL of the solvent (2-propanol/water mixture) were
introduced to the Schlenk tube. Next, the Schlenk tube was sealed
with a rubber septum and introduced into an oil bath preheated
these two liquid phases in such a system. Microspheres do not
have direct contact with the magnetic stirring element, so they are
not mechanically damaged. The reaction requires vigorous stirring
in order for the mixture to be evenly homogenized and for the
contact of the reactants to be facilitated.
ICP studies of the reaction mixture and the post-reaction prod-
uct extracts were done in order to assess the possible presence of
palladium leached from the carrier. The content of palladium in the
reaction products was below the detection limit.
◦
to 80 C. The reaction mixture was magnetically stirred at a given
temperature for 6 h. After each 1 h, 2 mL of the reaction mixture was
taken and extracted with 5 mL of diethyl ether. The extracts were
GC-FID analyzed with dodecane (0.010 mL) as an internal standard
to determine the conversion of aryl bromides.
3.4. Reuse of catalyst procedure
Because the catalyst floats on the surface of the water, it was
2.4. Kinetic studies
possible to remove the post-reaction remains (mainly residues of
boronic acids and bases) by pipetting. Subsequently, a new portion
of the starting materials was added to the Schlenk tube, and the
reaction was carried out under the conditions described above. The
recycling was performed ten times in a row for both bases.
To follow the kinetic properties of the Suzuki–Miyaura reac-
tion, two of the slowest reacting substrates (2-bromotoluene and
-bromotoluene) were selected (Fig. 11).
During these studies, the standard course of the reaction was
4
observed. After 4 h of the reaction, a ca. 60% conversion was
reached. To that point, the reaction was fast. After 4 h, the reaction
slowed down, reaching a ca. 70% conversion after 6 h. It should be
noted that, in the course of the reaction due to the necessity of sam-
pling, the ratio between the substrates and the catalyst changed.
After every hour, 1/6 of the substrate was lost, but the amount of
the catalyst did not change. These differences, however, had very
little effect on the reaction, and, after 6 h, a slightly higher conver-
sion of the substrates was obtained, but it was still close to that
obtained in the standard Suzuki–Miyaura reaction, 53% and 61%.
3.5. Separation of the catalyst for analysis and recycling
procedure
After several reactions, the catalyst was separated by filtration.
A pale gray solid was washed several times with water and diethyl
ether to remove all the reaction material and dried in an N flow. For
the recycling procedure, the catalyst recovered from five reactions
was weighed (20 mg) and added to the Suzuki–Miyaura reaction
under standard conditions. The catalyst was collected after the
reuse procedure and used for SEM and TEM analyses.
2
3
. Experimental
3.6. TEM
3.1. Synthesis of the palladium catalyst
TEM measurements were performed using a FEI Tecnai G2 20
Polymer microspheres (1.00 g) were placed in a 50 mL flask, and
0 mL of MeCN was added. In another flask, a solution contain-
X-TWIN electron microscope with LaB6 catode providing 0.25 nm
resolution. To the small sample of catalyst 2 mL of methanol were
added and the resulted mixture was ultrasonically treated for 5 min.
Specimens for TEM studies were prepared by putting a droplet of
a colloidal suspension on a copper microscope grid followed by
evaporating the solvent under IR lamp for 15 min.
1
ing 0.10 g of PdCl (MeCN)2 in 10 mL of MeCN was prepared. The
2
solution of the palladium complex was slowly added to the stirred
suspension of the polymer. When the entire amount of the solution
was added, the reaction was left stirred for 24 h at room temper-
ature. After that time, the product was filtered off, washed with
MeCN, DEE, and dried in vacuo.
The palladium content estimated by ICP was 0.0125 weight%,
which means that 10% of all nitrogen atoms in the sample are
associated with palladium.
3
.7. GC
GC-FID and GC–MS spectra of organic products were obtained
using HP 5890 (Hewlett Packard) instrument with mass detector
971 A. Capilary column HP 5 was used with non-polar liquid phase
containing 95% of dimethyl- and 5% of diphenyl-polysiloxane.
5
3
.2. Suzuki–Miyaura standard reaction procedure
Suzuki–Miyaura reactions were performed in a Schlenk tube.
Weighed amounts of the solid reactants: phenylboronic acids
3.8. ICP
(
(
1.1 mmol), base (2. mmol), catalyst (20.00 mg), aryl bromide
1 mmol), and 5 mL of the solvent (2-propanol/water mixture)
ICP measurements of palladium content were performed using
spectrometer ARL model 3410. Before analysis a weighted samples
of palladium catalyst were mineralized with 2 mL of aqua regia, left
for 7 days and diluted next to 10 mL with distilled water.
were introduced to the Schlenk tube. Next, the Schlenk tube was
sealed with a rubber septum and introduced into an oil bath pre-
heated to 80 C. The reaction mixture was magnetically stirred at a
◦

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