Highly active thiol-functionalized SBA-15 supported palladium catalyst for Sonogashira and Suzuki-Miyaura cross-coupling reactions

Article abstract of DOI:10.1039/c4ra13322f

Highly ordered mesoporous silica SBA-15 with pendent 3-mercaptopropyl groups has been prepared by condensation of surface silanols and (3-mercaptopropyl)trimethoxysilane. Treatment of the mercaptopropylated SBA-15 with (CH₃CN)₂PdCl₂ gave a heterogeneous Pd-catalyst. The immobilized Pd-catalyst served as an efficient heterogeneous catalyst for Sonogashira and Suzuki-Miyaura cross coupling reactions of aryl halides. Furthermore, the SBA-15 supported Pd-catalyst was recovered by a simple filtration from the reaction mixture and reused five times without significant loss of its catalytic activity. This journal is

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Highly Active Thiol-Functionalized SBA-15 Supported
Palladium Catalyst for Sonogashira and Suzuki-Miyaura
Cross-Coupling Reactions
Cite this: DOI: 10.1039/x0xx00000x
Shaheen M. Sarkar,* Md. Lutfor Rahman, Mashitah Mohd Yusoff
Received 00th January 2012,
Accepted 00th January 2012
Highly ordered mesoporous silica SBAꢀ15 with pendent 3ꢀmercaptopropyl group has been prepared by
condensation of surface silanols and (3ꢀmercaptopropyl)trimethoxysilane. Treatment of the
mercaptopropylated SBAꢀ15 with (CH3CN)2PdCl2 gave a heterogeneous Pdꢀcatalyst. The immobilized
Pdꢀcatalyst served as an efficient heterogeneous catalyst for Sonogashira and SuzukiꢀMiyaura cross
coupling reactions of aryl halides. Furthermore, the SBAꢀ15 supported Pdꢀcatalyst was recovered by a
simple filtration from the reaction mixture and reused five times without significant loss of its catalytic
activity.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Keywords: Heterogeneous, Immobilization, Palladium catalyst, Sonogashira coupling, Suzukiꢀ
Miyaura coupling, Thiolꢀfunctionalized SBAꢀ15.
procedures and the potential for reuse of the supported catalysts [62].
In particular, highly ordered nanostructured mesoporous silica SBAꢀ
1. Introduction
15 has extensively used as promising supports because it contains
high surface area, porosity, and lots of surface silanol groups [63ꢀ
66]. These features can offer environmentalꢀfriendly catalytic
systems as well as improved processing steps. The search for an
efficient, readily available and recyclable heterogeneous catalytic
system is still a major challenge [67ꢀ70].
Our current interest in this field led to us to explore the
immobilization of Pdꢀcatalyst onto SBAꢀ15 silica having nanopores.
Herein we report the synthesis and characterization of SBAꢀ15
supported Pdꢀcatalyst and illustrate its application for the
Sonogashira and SuzukiꢀMiyaura crossꢀcoupling reactions under
mild reaction conditions. The catalyst shows high catalytic activity
in the coupling reactions of various aryl halides. The ease
preparation of the catalyst, its long shelf life and its stability toward
air, and its compatibility with a wide variety of aryl halides make it
an ideal system for coupling reactions in aqueous phase.
Palladiumꢀcatalyzed CꢀC bondꢀforming reactions have played an
important role in synthetic organic chemistry [1]. The palladiumꢀ
catalyzed coupling of an aryl halide with aryl boronic acid (Suzuki
coupling) [2, 3] or terminal alkyne (Sonogashira coupling) [4ꢀ6] is
recognized as the most successful method for forming C(sp2)–C(sp2)
and C(sp)–C(sp2) CꢀC bond, respectively. These reactions shown
widespread applications in the synthesis of natural products,
biologically active molecules, and materials science [7ꢀ12]. Many
catalytic systems have been developed for the SuzukiꢀMiyaura and
SonogashiraꢀHagihara crossꢀcoupling reactions using different
palladium catalysts such as Pd(PPh3)4, but it is sensitive to air
oxidation and thus require airꢀfree conditions which pose significant
inconvenience on synthetic applications [13ꢀ15]. In addition,
Sonogashira coupling reactions, Glaserꢀtype oxidative dimerization
of the terminal alkynes cannot be avoided in copper mediated
reactions in which side products (diynes) are generally difficult to
separate from the desired products, while copper acetylide is a
potentially explosive reagent [16ꢀ21]. Many palladium catalysts used
in the SuzukiꢀMiyaura and SonogashiraꢀHagihara reactions are
homogeneous [22ꢀ25] catalysts, in spite of many advantages, are
impossible to be recovered and the residual palladium left in the
product confines their use in bioactive molecules and largeꢀscale
synthesis. In order to overcome these drawbacks, in recent years,
great efforts in catalysis research have been devoted to the
introduction and application of effective heterogeneous catalysts
[26ꢀ33]. In this context, ligandꢀfree palladium nanoparticles [34ꢀ39],
as well as different ligands like palladacycles [40ꢀ42], Nꢀ
heterocyclic carbene [43], Schiff bases [44ꢀ46], and dendrimers [47]
have been explored to be grafted on various inorganic and organic
supports such as mesoporous silica [48ꢀ52], ionic liquids [53, 54]
and polymers [55ꢀ61] for the preparation of heterogeneous catalysts.
Immobilization of catalysts to such solid supports opens the
possibility for extending the benefits of heterogeneous system to
homogeneous catalysts. The benefits may include ease of workꢀup
2. Experimental
2.1 General Information
All manipulations were performed under atmospheric
conditions otherwise noted. Reagents and solvents were obtained
from commercial suppliers and used without further purification.
Water was deionized with a Millipore system as a MilliꢀQ grade.
(CH3CN)2PdCl2 was purchased from Aldrich chemical industries,
Ltd. Proton nuclear magnetic resonance (1H NMR, 500/400 MHz)
and carbon nuclear magnetic resonance (13C NMR, 125 MHz)
spectra were measured with
a JEOL JNM ECAꢀ500/400
spectrometer. The 1H NMR chemical shifts were reported relative to
tetramethylsilane (TMS, 0.00 ppm). The 13C NMR chemical shifts
were reported relative to deuterated chloroform (CDCl3 77.0 ppm).
Elemental analyses were performed on a Yanaco CHN Corder MTꢀ6
elemental analyzer by the chemical analysis team in Rikagaku
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Kenkyūjo (RIKEN), Wako, Japan. Inductively coupled plasma mixture was diluted with EtOAc and the Pdꢀcatalyst 2 was separated
atomic emission spectrometry (ICPꢀAES) was performed on a by filtration. Organic layer was washed with water, dried over
Shimadzu ICPSꢀ8100 equipment by the chemical analysis team in MgSO4 and evaporated under reduced pressure. The residue was
RIKEN Wako, Japan. N2 adsorptionꢀdesorption isotherms were purified by short column chromatography on silica gel to give the
measured with a BEL SORP mini II analyzer at liquid N2 corresponding coupling products in up to 96% yield.
temperature. Surface area (SBET) was calculated by the BET method,
the pore volume (Vp) was determined by nitrogen adsorption at a
relative pressure of 0.98, and average pore size (D) was determined
3. Results and discussion
3.1. Characterizations of the SBAꢀ15 supported Pdꢀcatalyst 2
from the desorption isotherms using the BarrettꢀJoynerꢀHalenda
(BJH) method. The gas chromatographyꢀmass spectrometry (GCꢀ
MS) was measured by an Agilent 7860A/JEOL JMSꢀT100GC
equipped with a capillary column (DBꢀWax, 0.25 mm i.d. × 30 m or
HPꢀ1, 0.32 mm i.d. × 30 m). Thin layer chromatography (TLC)
analysis was performed on Merck silica gel 60 F254. Column
chromatography was carried out on silica gel (Wakogel Cꢀ300).
The immobilization of Pdꢀcatalyst onto nanostructured
2
mesoporous SBAꢀ15 silica was performed in two steps (Scheme 1).
Treatment of SBAꢀ15 silica with (3ꢀmercaptopropyl)triethoxysilane
in refluxing toluene for 12 h gave mercaptopropylated SBAꢀ15. The
incorporation of the 3ꢀmercaptopropyl precursor was confirmed by
elemental analysis and weight gain provided SBAꢀ15 supported
mercapto precursor 1 with loading ratio of 0.40 mmol/g. The SBAꢀ
2.2. Preparation of the mesoporous SBAꢀ15 silica
15 supported mercapto precursor
1 was then treated with
(CH3CN)2PdCl2 (0.2 mmol) in CHCl3 at 65 °C for 12 h. The
resultant brown color SBAꢀ15 supported Pdꢀcatalyst 2 was filtrated
on a glass filter, washed by CH2Cl2 and dried under vacuum at 65 °C
to give SBAꢀ15 supported Pdꢀcatalyst 2. Elemental analysis and
weight gain showed that 0.16 mmol of palladium complex was
anchored onto 1.0 g of 2. The loading amount (0.16 mmol/g) of Pdꢀ
catalyst 2 was further determined by ICPꢀAES analysis. Recently, L.
Dai et. al. [72] prepared sulfurꢀmodified SBAꢀ15 supported
amorphous palladium catalyst which efficiently promoted alcohol
oxidation reaction. From their report it is confirmed that the
palladium was strongly coordinate with the sulfur atoms.
Mesoporous silica SBAꢀ15 was synthesized as reported by Zhao
[71]. In a typical preparation procedure, 4 g of Pluronic P123 was
dissolved with stirring in 30 g of water and 120 g of 2 M HCI
solution at 35 °C. Then 8.5 g of TEOS was added into that solution
under stirring. The mixture was maintained at 35 °C for 10ꢀ12 h and
then at 60 °C for 48 h and then aged at higher temperature between
100 °C and 120 °C for 48 h under static conditions in a Teflonꢀlined
autoclave to generate materials with uniform pore diameter from 4 to
10 nm. The solid product was recovered and washed with DI water.
2.3. Preparation of the mercaptopropylated SBAꢀ15 silica 1
SBAꢀ15 silica (1.0 g) was added to a solution of (3ꢀ
mercaptopropyl)trimethoxysilane (94 mg, 0.48 mmol) in toluene (12
o
mL) and the mixture was stirred at 105 C for 12 h. The resultant
mesoporous powder was collected by filtration, washed repeatedly
with CH2Cl2 and dried under vacuo to afford (3ꢀ
mercaptopropyl)trimethoxysilanized SBAꢀ15 silica 1. Weight gain
showed that 0.4 mmol of (3ꢀmercaptopropyl)trimethoxysilane was
immobilized on 1.0 g of the SBAꢀ15.
2.4. Preparation of the SBAꢀ15 supported Pdꢀcatalyst 2
SBAꢀ15 silica 1 (1 g, 0.4 mmol) was added into a stirred
solution of bis(acetonitrile)dichloropalladium (51.9 mg, 0.2 mmol)
o
in CHCl3 (8 mL) and stirred for 12 h at 65 C. The reaction mixture
was filtered on a glass frit. The powder was washed with methylene
chloride and dried under vacuum at 65 oC to afford SBAꢀ15
supported Pdꢀcatalyst 2. Weight gain and ICP analyses were showed
that 0.16 mmol of Pdꢀcomplex anchored onto 1.0 g of SBAꢀ15 silica
2.
Scheme 1 Preparation of the SBAꢀ15 supported Pdꢀcatalyst 2
The TEM images were obtained before and after modification of
the SBAꢀ15 silica (Fig. 1 & 2, ESI). Both images showed that the
hexagonal symmetry of the pore arrays is conserved after
immobilization of the Pdꢀcomplex onto the SBAꢀ15 silica. The
smallꢀangle Xꢀray diffraction patterns of SBAꢀ15 shows a strong
diffraction peak at 100 and two small diffraction peaks at 110 and
200 planes (Fig. 3, ESI). The presence of guest moieties on the
mesoporous framework of SBAꢀ15, resulting in the decrease of
intensity of the peaks. The narrow pore size distribution
demonstrating a uniform mesoporosity of the SBAꢀ15 supported Pdꢀ
catalyst 2. The structural information about the Pdꢀcatalyst 2, the N2
sorption isotherm plot show a typeꢀIV isotherm with a H2 hysteresis
loop, indication that the Pdꢀcatalyst 2 still maintains a good
mesoporous cageꢀlink structure (Fig. 4, ESI). The BET surface area
and pore volume of SBAꢀ15 is 750 m2/g and 0.83 cm3/g, whereas in
Pdꢀcatalyst 2, this volume decrease to 465 m2/g and 0.38 cm3/g,
respectively (Table 1, ESI). The surface area, pore volume and pore
2.5. General procedure for the Sonogashira reaction
Aryl halide (1 mmol), phenylacetylene (1.1 mol equiv), base (2
mol equiv) and the Pdꢀcatalyst 2 (7 mg, 0.1 mol%) was stirred at 75
°C for 1 h. The reaction mixture was cold at room temperature and
diluted with EtOAc and the immobilized Pdꢀcatalyst was separated
by filtration. The organic layer was washed by H2O, dried over
MgSO4 and evaporated under reduced pressure. The residue was
purified by short column chromatography on silica gel eluted with nꢀ
hexane/EtOAc to afford the corresponding coupling products in up
to 98% yield.
2.6. General procedure for the Suzuki reaction
A mixture of aryl halide (1 mmol), boronic acid (1.1 mol equiv),
K2CO3 (2 mol equiv), and the Pdꢀcatalyst 2 (0.1 mol%) in 50%
aqueous ethanol (1.5 mL) was stirred at 90 ºC for 6 h. The reaction
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size in Pdꢀcatalyst 2 are reduced during the functionalization of Pdꢀcatalyst 2. In order to test the reusability, we carried out the
organic moiety onto the parent SBAꢀ15.
coupling reaction of iodobenzene in the presence of 0.1 mol% of Pdꢀ
catalyst 2.
3.2. Sonogashira crossꢀcoupling reaction
Table 2. Sonogashira coupling reaction with SBAꢀ15 supported Pdꢀ
catalyst 2a
We then investigated the catalytic efficiency of Pdꢀcatalyst 2 in the
Sonogashira crossꢀcoupling reaction without presence of copper and
solvent. The Sonogashira crossꢀcoupling of aryl halide and terminal
alkyne is a useful tool for the synthesis of arylꢀsubstituted acetylene.
This method has been widely used for the synthesis of natural
products, biologically active molecules [73] nonlinear optical
materials and molecular electronics [74] dendrimeric and polymeric
materials [75] macrocycles with acetylene links [76] and
polyalkynylated molecules [77]. With the heterogeneous Pdꢀcatalyst
2 in hand, the Sonogashira coupling reaction was carried out using
iodobenzene with phenylacetylene in the presence of Et3N. The
supported Pdꢀcatalyst 2 (0.1 mol%) efficiently promoted the
Sonogashira crossꢀcoupling reaction under solvent and copper free
reaction conditions to give the corresponding coupling product in
92% yield (Table 1, entry 1). Then we performed the reaction using
(i-pr)2EtN and piperidine and found piperidine is the best effective
base in this crossꢀcoupling reaction.
2 (0.1 mol%)
X +
Ph
Ph
piperidine
75 °C, 1 h
R
R
X = I/Br
3
Ph MeO
Ph Me
Ph
3a
3b
3c
X = I, 98%
X = I, 92%
X = I, 95%
X = Br, 96%
X = Br, 89%
X = Br, 92%
O
Ph
Ph
O2N
Ph NC
Ph
3d
3e
3f
X = I, 97%
X = Br, 94%
X = I, 96%
X = Br, 95%
X = I, 98%
X = Br, 95%
3g X = I, 91%
X = Br, 88%
F3C
aMolar ratio: aryl halide (1 mmol), Pdꢀcatalyst
phenylacetylene (1.1 mol equiv) and piperidene (2 mol equiv).
2 (0.1 mol%),
Table 1. Sonogashira coupling reaction with SBAꢀ15ꢀsupported Pdꢀ
catalyst 2a
2 (0.1 mol%)
After completion of the reaction, it was diluted with EtOAc and
the SBAꢀ15 supported Pdꢀcatalyst 2 was recovered from the reaction
mixture by simple filtration, washed with EtOAc and used it for the
next cycle without changing the reaction conditions. It is noteworthy
that the catalyst could be used six times without significance loss of
its activity (Fig. 1).
I
+
Ph
Ph
base, 75 °C, 1 h
3
Entry
Base
Conv. (%)b
1
2
3
Et3N
92
95
100
80
60
40
20
0
(i-pr)2EtN
piperidine
100
aMolar ratio: aryl halide (1 mmol), Pdꢀcatalyst 2 (0.1 mol%,
loading ratio = 0.16 mmol/g), phenylacetylene (1.1 mol equiv) and
base (2 mol equiv). bDetermined by GC analysis.
Due to the high catalytic activity of the SBAꢀ15 supported Pdꢀ
catalyst 2 we then extended the scope of the Sonogashira coupling
reaction using different aryl halides. Excellent catalytic activity was
observed in the couplings of iodobnzene, deactivated 4ꢀiodoanisole
and 4ꢀiodotoluene (Table 2, 3a-c, X = I, isolated yield) as well as
activated
4ꢀiodoacetophenone,
4ꢀiodoꢀnitrobenzene,
4ꢀ
cyanoiodobenzene and 4ꢀIodobenzotrifluoride (3d-g, X = I). The
deactivated aryl iodides possessing electronꢀdonating group showed
a slight drop in reactivity compared to the activated aryl iodides
possessing electronꢀwithdrawing group. It is worthy to note that the
immobilized Pdꢀcatalyst 2 showed remarkably catalytic activities in
the coupling of bromobenzene and substituted bromobenzenes to
give the corresponding coupling products (3a-g, X = Br) in up to
96% yield with 100% selectivity.
1
2
3
4
5
6
Run
Fig. 1. Recycling of the SBAꢀ15ꢀsupported Pdꢀcatalyst 2
Recently, B. Movassagh et al [46] reported Pd(II) Schiff base
complex supported on multiꢀwalled carbon nanotubes for
Sonogashira crossꢀcoupling reaction of aryl iodide using 1.2 mol%
of Pd under copper free reaction conditions with prominent
decreased of the catalytic activity (1st cycle 99, 4th cycle 82%).
However our catalyst efficiently (0.1 mol%) promoted the
Sonogashira reaction (twelve times faster) without significance loss
of its catalytic activity (1st cycle 100, 4th 96%).
3.3. SuzukiꢀMiyaura crossꢀcoupling reaction
The palladiumꢀcatalyzed Suzuki crossꢀcoupling of aryl halides with
arylboronic acids has become a general and convenient synthetic
route in organic chemistry toward biaryls, which has been employed
in many areas of organic synthesis, including natural product
synthesis. By observing the high catalytic activity of SBAꢀ15
supported Pdꢀcatalyst 2 in the Sonogashira reaction hence, we
explore the catalytic activity of SuzukiꢀMiyaura crossꢀcoupling
reaction of aryl halides under mild reaction conditions. With the
heterogeneous Pdꢀcatalyst 2 (0.1 mol%), we then tested Suzukiꢀ
The reusability of immobilized Pdꢀcatalyst is one of the
important factors for practical application of heterogeneous catalyst.
We then turn attention to recover and reuse of the SBAꢀ15 supported
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Miyaura cross coupling reaction of 4ꢀiodoanisole with
phenylboronic acid in aqueous ethanol at 90 ºC to give the
corresponding biaryl product in 96% isolated yield (Table 3, 4a).
High catalytic activity was observed in the coupling of deactivated
aryl iodides such as 4ꢀiodotoluene, 4ꢀiodophenol and 4ꢀiodoaniline
(4b-e) as well as activated 4ꢀiodoacetophenone and 4ꢀ
cyanoiodobenzene (4f, g). In order to investigate the scope of aryl
halides with phenylboronic acid, various aryl bromides were used.
The coupling of activated or deactivated aryl bromides cleanly
proceeded with 0.1 mol% of Pdꢀcatalyst 2 (4a-g) to give the
corresponding coupling products in up to 94% isolated yield. It is
notable that, aryl chloride was also coupled with phenylboronic acid
to give the biaryl products in up to 54% yield (4f, g). Recently, A. C.
Sullivan et al [78] reported palladium ethylthioglycolate modified
silica as a heterogeneous catalyst for SuzukiꢀMiyaura cross coupling
reaction of aryl bromide in xylene using 5 mol% of palladium where
the catalytic activity is dramatically decreased (1st cycle 99, 3rd cycle
90%). Here we used only 0.1 mol% of catalyst which showed better
catalytic activity in aqueous ethanol as well as reusability of the
catalyst (1st cycle 99, 3rd cycle 98%).
S
S
Pd(II)
Cl
Cl
EtOH/H2O
Me
O
O
Cl
S
S
Pd(0)
Me
Suzuki Reaction
S
S
S
S
Pd(II)
Pd(II)
Cl
O
O
Me
B(OH)2
Me
ClB(OH)2
Scheme 2 Plausible mechanism of Suzuki coupling reaction
Table 3. SuzukiꢀMiyaura coupling reaction with SBAꢀ15ꢀsupported heterogeneous conditions still remains an open question. In order to
Pdꢀcatalyst 2a
determine whether the catalysis was due to the SBAꢀ15 supported
Pdꢀ complex 2 or to a homogeneous palladium complex that comes
off the support during the reaction and then returns to the support at
2 (0.1 mol%)
+
X
B(OH)2
K2CO3
EtOH/H2O (1:1)
90 °C, 6 h
the end (release and recapture mechanism), we performed the Pd
leaching test. To determine the Pd content in the solution, a part of
the filtrate (4a, X = I, after solvent removal) was placed in a 20 mL
crucible, heated to 600 °C at a heating rate of 10 °C/min, and then
calcined at 600 °C for 3.5 h. The residue was dissolved in 15 mL
aquaꢀregia and diluted to 20 mL. The Pd leaching in solution was
determined by inductively coupled plasma mass spectrometry (ICPꢀ
MS) analysis. It revealed that the leaching of Pd from the catalyst
into the solution was lower than 0.21 ppm after six consecutive run,
which suggests the heterogeneous nature of the prepared SBAꢀ15
supported Pdꢀcatalyst 2.
R'
R'
R
R
4
X = I/Br/Cl
MeO
Me
HO
4a: X = I, 96%
4b: X = I, 93%
X = Br, 90%
4c: X = I, 92%
X = Br, 91%
X = Br, 88%
Me
H2N
Me
Me
O
4f: X = I, 97%
4d: X = I, 90%
4e: X = I, 91%
X = Br, 92%
X = Cl, 54%
X = Br, 87%
X = Br, 89%
4g: X = I, 96%
X = Br, 94%
X = Cl, 51%
NC
100
80
60
40
20
0
aMolar ratio: aryl halide (1 mmol), Pdꢀcatalyst 2 (0.1 mol%), boronic
acid (1.1 mol equiv), K2CO3 (2 mol equiv), EtOH/H2O ( 1.5 mL).
In general, Suzuki coupling reactions catalyzed by solidꢀsupported
Pd follow the usual reaction mechanism (similar to homogenous
catalysis, Scheme 2), but the full understanding of mechanism in
1
2
3
4
5
6
Run
Fig. 2. Recycling of the SBAꢀ15 supported Pdꢀcatalyst 2
4. Conclusion
In conclusion, we have developed nanostructured SBAꢀ15ꢀsupported
Pdꢀcatalyst 2 for Sonogashira and SuzukiꢀMiyaura crossꢀcoupling
reactions. The heterogenized Pdꢀcatalyst was found to be highly
active catalyst for these coupling reactions of aryl iodide, bromide as
well as chloride system. The Sonogashira crossꢀcoupling reaction
was performed without presence of copper and solventꢀfree reaction
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reused without significant loss of its activity.
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Acknowledgement
We gratefully acknowledge the finical support of the University
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DOI: 10.1039/C4RA13322F
Graphical abstract:
SBA-15 supported Pd-catalyst was synthesized and characterized. The catalyst showed high
activity (0.1 mol %) towards Sonogashira and Suzuki-Miyaura cross-coupling reactions of
activated and deactivated aryl halides under mild conditions. The catalyst was readily recovered
and used six times without significant loss of its catalytic activity.
R
SBA-15
supported
Pd-catalyst
X
+
R
B(OH)2
X = I/Br/Cl
R'
R
R'