Highly water-dispersible magnetite nanoparticle supported-palladium-β-cyclodextrin as an efficient catalyst for Suzuki-Miyaura and Sonogashira coupling reactions

Article abstract of DOI:10.1039/c6ra04575h

We reported here a novel highly water-dispersible and recoverable magnetite supporting a palladium-β-cyclodextrin complex as an efficient catalyst in Suzuki-Miyaura and Sonogashira carbon-carbon coupling reactions. The magnetite nanoparticle supporting catalyst was characterized by FT-IR, CHN, EDS, TGA, XRD, TEM and VSM. The prepared catalyst displayed excellent activity for a wide range of substrates in aqueous solution under mild reaction conditions. The reusability of the magnetite supporting palladium-β-cyclodextrin nanocatalyst was successfully examined five times with a slight loss of catalytic activity.

Full text of DOI:10.1039/c6ra04575h

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DOI: 10.1039/C6RA04575H
Journal Name
ARTICLE
Received 00th January
2
0xx,
Highly Water‐dispersible Magnetite Nanoparticles Supported‐
Palladium‐‐Cyclodextrin as Efficient Catalyst for Suzuki‐Miyaura
and Sonogashira Coupling Reaction
a
a
a
b
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
H. Salemi, B. Kaboudin,* F. Kazemi and T. Yokomatsu
We reported here a novel highly water‐dispersible and recoverable magnetite supporting a palladium‐‐cyclodextrin
complex as an efficient catalyst in Suzuki‐Miyaura and Sonogashira carbon‐carbon coupling reactions. The magnetite
nanoparticles supporting catalyst was characterized by FT‐IR, CHN, EDS, TGA, XRD, TEM and VSM. The prepared
catalyst displayed excellent activity for wide range of substrates in aqueous solution under mild reaction conditions. The
reusability of magnetite supporting palladium‐‐cyclodextrin nanocatalyst was successfully examined five times with a
slight loss of catalytic activity.
Introduction
attracted much attention in developing greener catalytic reactions.
The magnetite‐supported catalysts with high catalytically active
surface areas, low porosity and readily dispersed in the reaction
Transition metal‐catalyzed carbon–carbon bond formation
reactions are important methodologies in catalytic coupling
reactions because they facilitate key steps in synthesis of many
significant products in the commercialized or development
system are well accessible to the reactants. Also, magnetic
nanoparticles can be simply removed from the reaction medium by
an external magnet readily without spending much time and
1
1d, 12
1
laborious separation steps.
During the past years, many attempts have been focused on the
phase.
Palladium‐catalyzed carbon‐carbon coupling of aryl
halides/triflates with arylboronic acids as reagents with
nontoxic nature, high stability to air, heat and moisture
emerged as extremely powerful tools in biaryl synthesis during
the past decade. The significant reactions are generally called
the Suzuki‐Miyaura reaction. In addition to the reaction,
palladium‐catalyzed Sonogashira coupling is also one of the most
important catalytic reactions for the formation of sp ‐sp carbon‐
carbon coupling between alkenyl or aryl halides/triflates and
13
homogeneous catalysts with water‐soluble ligand. Traditional
strategy for obtaining a water‐soluble catalyst is to modify ligands
1
4
with
a hydrophilic functional 16group such as sulfonates ,
1
5
1
7
carboxylates , ammonium salts
and polyethylene glycol.
2
Although preparation of water dispersible magnetite nanoparticles
through surface modification with hydrophilic groups have been
1
8
2
pursued by many research groups for bio‐related applications , the
surface‐modified magnetite as solid supports with hydrophilic
groups have been recently developed by us for Pd‐catalyzed
3
terminal alkynes.
1
9
coupling reactions in neat water. In our continuous interests in
developing a greener metal‐catalyzed reaction, we have also
focused on β‐cyclodextrin (β‐CD) as a greener supramolecular
compound.
Improvements in these catalytic coupling reactions have led to a
great interest in the increased reactivity and stability of the metal
catalysts by use of efficacious supporting ligands such as
4
5
6
7
phosphines , N‐heterocyclic carbenes , Palladacycles and others.
β‐CD is a water‐soluble, low price and semi natural cyclic
oligosaccharide possessing a hydrophobic cavity that can bind
substrates selectively. The reversible formation of the host–guest
complexes by non‐covalent bondings in the cavity could be a good
chance for catalytic reactions upon installation of transition metals
However, drawbacks for their attaching and removing, and
environmental concerns cause many attempts to overcome these
issues. To overcome these problems, many attentions have been
directed toward the development of new methods to immobilize
the homogeneous palladium catalysts onto various solid supports
2
0
8
9
10
to the cavity. Consequently, catalytic coupling reactions on the
basis of this green supramolecular have been the focus of many
such as silica , metal–organic framework , polymers and metal
1
1
oxides which is easier to separate and recycle the catalyst without
much problems of metal pollution in the final products.
2
1
II
investigations. In this context, we have also developed the Cu ‐‐
Cyclodextrin complexes which work as homogeneous or
heterogeneous catalyst in homo‐ and cross‐coupling of arylboronic
In recent years magnetite nanoparticle‐supported catalysts have
2
2
acids.
a.
Due to importance of heterogeneous catalyst from environment
concerns, specifically magnetically separable catalyst in water
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, 1432‐1
without use of any additives such as phosphine ligand or phase
b.
23
transfer reagent,
we have designed and synthesized the
Horinouchi, Hachioji, Tokyo 192‐0392, Japan.
II
hydrophilic Pd ‐‐Cyclodextrin complex (MNP‐CD‐Pd) anchored on
3‐aminopropyltriethoxysilane‐functionalized magnetite
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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nanoparticles as a highly water dispersible heterogeneous catalyst washed with deionized water repeatedly and dried in vacuum oven.
View Article Online
‐
1
‐1
having the hydrophobic cavity for carbon‐carbon coupling reaction FT‐IR (KBr, cm ): 570, 1123, 1624, 3400 cm D.OI: 10.1039/C6RA04575H
in aqueous solutions. In this paper we now disclose the
characterization and reactivity of MNP‐CD‐Pd directing toward the Functionalization of Fe O with 3‐aminopropyltriethoxysilane
3
4
Suzuki‐Miyaura coupling reaction and the Sonogashira reaction.
(MNP‐AP)
Magnetite nanoparticles (MNP, 1g) were dispersed in dry toluene
20 mL) by sonicaꢀon for 30 min and then 3‐
aminopropyltriethoxysilane (APTES, 2 mL) was added to the
resulꢀng mixture. The mixture was refluxed for 24 h under argon
atmosphere. Aꢁer 24 h, the funcꢀonalized magnetite nanoparticles
(
Experimental
General
All reagents and solvents were purchased from commercial
suppliers. NMR spectra were recorded at 25°C on a Bruker Avance
(
MNP‐AP) were separated by an external magnet, washed
thoroughly with ethanol and distilled water, and dried under
vacuum oven. FT‐IR (KBr, cm ): 570, 1050, 1123, 2917, 1560, 3400
cm .
1
13
4
00 NMR Spectrometer ( H NMR: 400 MHz; C NMR: 100 MHz).
‐1
Gas chromatography was performed with a Varian CP 3800
chromatograph. Analytical TLC was carried out with Merck plates
precoated with silica gel 60 F254 (0.25 mm thick).
Thermogravimetric analysis was conducted from room temperature
to 800 °C in an oxygen flow using a NETZSCH STA 409 PC/PG
instrument. A Varian spectrum 110 atomic absorpꢀon spectrometry
was used to investigate the content of palladium in the catalyst. FT‐
IR spectra were obtained using a Bruker Vector 22 instrument with
samples prepared as KBr pallets. The magnetic properties of the
prepared magnetite nanoparticles were measured with a Vibrating
Sample Magnetometer (Meghnatis Daghigh Kavir Company, Iran) at
room temperature from −10 000 to +10 000 Oe. Transmission
electron microscopy (Philips CM30 TEM) and powder X‐ray
Diffraction pattern were used to investigate the structure and
morphology of the prepared materials. Elemental analyses were
performed by the Elemental Vario EL III.
‐1
Preparation of MNP‐CD‐Pd catalyst
For preparation of magnetite supported palladium‐‐cyclodextrin
catalyst (MNP‐CD‐Pd), MNP‐AP (0.5 g) was dispersed in DMF (10
mL) for 30 min using ultrasound. Ts‐Pd‐‐CD (50 mg) was added to
the mixture and the mixture was sꢀrred at 80 °C for 24 h. Aꢁer 24 h
MNP‐CD‐Pd was separated by an external magnet and repeatedly
washed with distilled water/ethanol and then dried under vacuum
‐1
‐1
oven. FT‐IR (KBr, cm ): 580, 1031, 1156, 1250, 2926, 3406 cm .
General procedure for Suzuki‐Miyaura coupling reaction with
MNP‐CD‐Pd catalyst
To a mixture of MNP‐CD‐Pd (0.03‐0.15 mol% based on palladium)
2 3
and K CO (0.30 mmol) in water (2 mL), aryl halide (0.2 mmol) and
arylboronic acid (0.24 mmol) were added and the mixture was
stirred at reflux condition at 100 °C. The reaction progress was
monitored by TLC and GC until the completion of the reaction.
Then, the product was extracted by n‐Hexane (2×3 mL). The
combined organic phases were concentrated. The residue was
purified with column chromatography to give coupling product,
Synthesis of Palladium‐‐Cyclodextrin complex
II
Palladium‐‐Cyclodextrin (Pd ‐‐CD) complex was prepared in an
II
analogues manner for previous preparation of Cu ‐‐CD with slight
2
2a
modification. Palladium acetate (3 mmol, 0.673 g) was added to a
soluꢀon of NaOH (0.5 M, 50 mL) and β‐cyclodextrin (1 mmol, 1.135
g). The mixture was sꢀrred at ambient temperature for 12 h and a
light yellow solution was prepared after dissolving the palladium
acetate. Aꢁer 12 h ethanol (500 mL) was added to this soluꢀon unꢀl
the light yellow suspension was formed. Then these precipitates
were filtrated and washed with ethanol and air‐dried at ambient
1
13
which was characterized with H and CNMR. MNP‐CD‐Pd
remaining in aqueous phase was separated by an external magnet,
washed thoroughly with ethanol and distilled water and dried
under vacuum oven. All coupling products gave satisfactory spectral
1
data in accord with the assigned structures. For example: 3a: H
NMR (400 MHz, CDCl
3
): δ (ppm) = 3.89 (3H, s), 7.01 (2H, d), 7.33
II
1
3
temperature. The prepared Pd ‐‐CD complex was characterized by
(1H, t), 7.45 (2H, t), 7.55 (4H, m). C NMR (100 MHz, CDCl
3
): δ
1
atomic absorption, EDS and H NMR (see supporting information),
(
ppm) = 55.4, 114.2, 126.7, 126.7, 128.2, 128.7, 133.8, 140.8, 159.1.
1
which confirmed the presence of palladium in the complex.
3
7
1
b: H NMR (400 MHz, CDCl ): δ (ppm) = 7.39 (2H, t), 7.49 (4H, t),
3
13
3
.65 (4H, d). C NMR (100 MHz, CDCl ): δ (ppm) = 127.2, 127.3,
Preparation
of
mono‐6‐O‐(p‐toluenesulfonyl)‐Palladium‐‐
28.8, 141.2.
Cyclodextrin (Ts‐Pd‐‐CD)
II
Pd ‐‐CD (1 g) was dissolved in 20 mL of sodium hydroxide solution General procedure for Sonogashira coupling reaction with MNP‐
0.5 M). p‐Toluenesulfonyl chloride (0.95 g, 5 mmol) was added to CD‐Pd catalyst
that solution and the mixture was stirred at room temperature for To a mixture of MNP‐CD‐Pd (0.075‐0.15 mol% based on palladium)
h. Aꢁer 4 h reacꢀon mixture filtrated and 500 mL ethanol was and K CO (0.40 mmol) in 2 mL H O/DMF, aryl halides (0.20 mmol)
(
4
2
3
2
added to filtrated solution to precipitate Ts‐Pd‐‐CD. The resulting and terminal alkyne (0.24 mmol) were added, and sꢀrred at 100‐
2
1i,24
precipitate was filtered and dried in vacuum oven.
Appearance 120 °C. The reacꢀon progress was monitored by TLC and GC. Aꢁer
O confirmed completion of the reaction, the product was extracted by ethyl
acetate (2x3 mL). The combined organic phases were concentrated.
1
of aromatic hydrogen peaks in H NMR in D
2
II
successfully tosylation of Pd ‐‐CD complex.
The residue was purified with column chromatography to give
coupling products, which were characterized with H and C NMR.
1
13
Preparation of Fe
3
O
4
nanoparticles (MNP)
The magnetite nanoparticles were prepared by traditional chemical MNP‐CD‐Pd remaining in aqueous phase was separated by an
2
5
co‐precipitation method. FeCl
g) were dissolved in 40 mL disꢀlled water under sꢀrring at 90 °C and water and dried under vacuum oven. All coupling products gave
continuous flow of argon gas Subsequently, 10 mL of ammonia satisfactory spectral data in accord with the assigned structures. For
25%) was added drop‐wise to the reaction mixture with intense example: 6a: H NMR (400 MHz, CDCl ): δ (ppm) = 7.29‐7.42 (6H,
3 2 2 2
.6H O (2.36 g) and FeCl .4H O (0.86 external magnet, washed thoroughly with ethanol and distilled
.
1
(
3
1
3
stirring. Prepared nanoparticles were magnetically separated and m), 7.56‐7.59 (4H, m) C NMR (100MHz, CDCl ): δ (ppm) = 89.40,
3
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1
1
23.30, 128.28, 128.37, 131.64. 6b: H NMR (400 MHz, CDCl
3
): δ
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(
ppm) = 2.40 (3H, s), 7.19 (2H, d), 7.35‐7.37 (3H, 3), 7.46 (2H, d),
DOI: 10.1039/C6RA04575H
1
3
7
8
1
.53‐7.55 (2H m). C NMR (100 MHz, CDCl ): δ (ppm) = 21.54,
3
8.73, 89.57, 120.20, 123.50, 128.10, 128.34, 129.19, 131.52,
31.57, 138.41.
Results and discussion
The magnetite nanoparticle‐supported Pd‐‐Cyclodextrin catalyst
prepared with following the procedure that shown in Scheme 1.
Firstly Pd‐‐Cyclodextrin complex was prepared by as same
II
22a
procedure for the preparation of Cu ‐‐CD.
The complex
formation of the Pd(II) with ‐cyclodextrin was also estimated by
1
the H NMR analysis of Pd(II)‐‐CD complex. As shown in Figure s2,
1
the H NMR (400 MHz) of the complex shows significant signal
broadening as a consequence of the presence of Pd(II) bonded to ‐
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 complex was tosylated using p‐
21i
toluenesulfunyl chloride in sodium hydroxide solution readily.
Secondly, magnetite nanoparticles (MNP) prepared with co‐
precipitation of Fe salts with ammonia and functionalized with 3‐
2
5
aminopropyltriethoxysilane (MNP‐AP). Finally, MNP‐CD‐Pd was
Figure 1 FT‐IR spectra (a) MNP (b) MNP‐AP (c) MNP‐CD‐Pd
prepared by a simple condensation between MNP‐AP and Ts‐Pd‐‐
CD. The supported catalyst can be homogeneously dispersed in Also, elemental analysis (Table 1) for MNP‐AP and MNP‐CD‐Pd
water to produce a brown solution. The prepared catalyst was confirm successfully grafting of organic groups on manganite
characterized by FT‐IR, CHN, EDS, TGA, XRD, TEM, VSM and atomic nanoparticles surface. The content of Pd in MNP‐CD‐Pd was
absorption spectrometry.
measured by atomic absorpꢀon spectrometry (0.062 mmol of pd
per one gram of the catalyst). Moreover, the electron‐dispersive X‐
ray (EDS) spectrum exhibited the presence of carbon, silicon and
specially palladium in the structure of MNP‐CD‐Pd catalyst that
confirmed catalyst preparaꢀon successfully (Figure 2).
Table 1 Elemental analysis
Nanoparticles
MNP‐AP
N (Weight%)
2.471
C (Weight%)
7.041
H (Weight%)
1.623
MNP‐CD‐Pd
2.155
8.059
1.326
Scheme 1 Schematic route for the Preparation of MNP‐CD‐Pd
Figure 1 shows FT‐IR spectra for magnetite nanoparticle and
‐1
funcꢀonalized nanoparꢀcles. It shows sharp peak at 570 cm
correspond to the Fe‐O stretching frequency and a strong broad
‐
1
band at 3400 cm is assigned hydroxyl stretching vibration for MNP
Figure 2 EDS spectrum of prepared MNP‐CD‐Pd catalyst
‐
1
(
Figure 1a). Appearance absorpꢀon bands at 2917 cm (aliphatic C‐
‐1
H groups) and at 1050 cm (Si‐O group) in MNP‐AP spectra indicate
magnetite nanoparticles functionalization has been done
successfully (Figure 1b). For MNP‐CD‐Pd spectra additional peak at
‐
1
1215 cm and increase absorption intensity of aliphatic C‐H groups
confirm immobilization of Pd‐‐CD on the magnetite nanoparticles
successfully.
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The XRD paꢂerns (Figure 5) of MNP, MNP‐AP andViewMANrtiPc‐leCODn‐lPinde
exhibits diffraction peaks corresponding tDoOIt:h1e0.1s0t3a9n/Cda6RrdA0s4p5i7n5eHl
cubic Fe O paꢂern (JCPDS card No. 79‐0417) and no peaks
3 4
characteristic for palladium nanoparticles were observed in MNP‐
CD‐Pd. The average crystallite sizes estimated using Scherrer’s
equation is 13 nm for MNP‐CD‐Pd.
Figure 3 Thermogravimetric analysis (a) MNP (b) MNP‐CD‐Pd
Figure 5 XRD patterns of (a) MNP (b) MNP‐AP (c) MNP‐CD‐Pd
Thermogravimetric analysis (TGA) of MNP and MNP‐CD‐Pd (Figure
3
) was proved the presence of aminopropyl and ‐cyclodextrin on The magnetic properties of nanoparticles were investigated with a
the surface of magnetite nanoparticles. According to TG analysis, Vibrating Sample Magnetometer (VSM). Figure 6 shows the
the total weight loss of MNPs over the full temperature range magnetic hysteresis loops of MNP, MNP‐AP and MNP‐CD‐Pd in an
◦
of 30–400 C was esꢀmated to be 2.0 wt% due to the loss of applied magneꢀc field of 10000 Oe at room temperature. Prepared
the adsorbed water as well as dehydration of the surface OH magnetite nanoparticles show superparamagnetic behavior with no
groups (Figure 3a). For MNP‐CD‐Pd the TGA curve shows two remaining effect from the hysteresis loops with removing the
considerable weight loss steps that second step in the range of 400‐ applied magnetic field. However functionalization of nanoparticles
5
20 °C related to ‐cyclidextrin decomposition (Figure 3b).
(MNP‐AP and MNP‐CD‐Pd) affected the saturation magnetization of
Structure and morphology of the catalyst was determined by X‐Ray these magnetite nanoparticles, because of the two coating layers of
reflective diffraction (XRD) and transmission electron microscopy APTES and Pd‐‐Cyclodextrin.
(TEM). The TEM image in Figure 4 shows that the MNP‐CD‐Pd
nanoparticles are of nearly spherical shape with mean diameter of
about 25 nm.
Figure 6 Magnetic hysteresis loops of (a) MNP (b) MNP‐AP (c) MNP‐CD‐Pd
The catalytic behavior of prepared MNP‐CD‐Pd was investigated for
the synthesis of biaryls from aryl boronic acids and aryl halides
(Suzuki‐Miyaura reacꢀon). The reacꢀon of 4‐bromoanisole and
phenyl boronic acid was used as model reaction for optimization of
Suzuki‐Miyaura coupling reacꢀon (Table 2). At the outset,
commonly uꢀlized bases were tested with 0.15 mol% of the catalyst
in water at 100 °C for 4h (entry 1‐8). The best result was observed
Figure 4 TEM images of MNP‐CD‐Pd
2 3
for K CO in water (entry 3). Subsequently, we try to decrease
catalyst amount and temperature, but we weren’t found promising
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results (entry 9‐13). So, K
catalyst at 100 °C for 6 h selected as an opꢀmal reacꢀon condiꢀon.
2 3
CO base in water and 0.15 mol% of the The homo‐coupling of boronic acid as byproduct was Vnieowt AsritgicnleifOicnalinnet
under this condition.
DOI: 10.1039/C6RA04575H
Table 2 Optimization of the Suzuki‐Miyaura coupling reaction in the Under the above optimized conditions, cross‐coupling reaction of
presence of MNP‐CD‐Pd
aryl halides with large scope of aryl boronic acids was studied in the
MNP-CD-Pd
MeO
Br
+
B(OH)2
presence of MNP‐CD‐Pd catalyst (0.03‐0.3 mol% Pd) (Table 3). In
general, most of the products were obtained in good to excellent
yield with high TONs within 4‐24 h. As expected aryl iodides and
bromides react efficiently with aryl boronic acids in the presence of
MNP‐CD‐Pd (0.03‐0.15 mol% of the catalyst) whiꢀn 4‐12 h (Table 3,
entry 1‐25). MNP‐CD‐Pd catalyst shows high selecꢀvity for 1‐chloro‐
MeO
base (0.3 mmol)
Solvent (2mL)
0.2 mmol
0.24 mmol
4h
Cat.
Yield
(%)
Entry
Base
Solvent
a
T (°C)
b
(
mol%)
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.075
0.03
0.015
0.15
0.15
0.15
1
2
3
4
5
6
7
8
9
NaOH
H
H
H
2
2
2
O
O
O
100
100
100
100
100
100
reflux
100
100
100
100
80
69
71
87
16
63
52
70
67
75
76
55
60
18
96
Cs
2
CO
CO
Na CO
3
4‐iodo‐benzene (entry 10). Treatment of aryl halides with a variety
K
2
3
of electron‐withdrawing, electron‐donating groups and heteroaryl
compounds of arylboronic acids gave the corresponding products in
good to high yield. Electron‐withdrawing functional groups in aryl
halides increase the reactivity and electron‐donating groups
decrease the reacꢀvity. Treatment of 2‐substituted aryl iodide with
phenyl boronic acid (entry 11) gives the corresponding biaryl in high
yield, but treatment of iodobenzene with 2,6‐dimethylphenyl
boronic acid (entry 8) gave only 10% of desired product aꢁer 24 h in
2
3
H2O
K
3
PO
4
H
H
2
O
O
Et
3
N
2
K2CO
3
3
3
3
3
3
3
3
H2O/MeOH
K
K
2
2
CO
CO
2
H O/DMF
2
H O
H2O
1
0
1
2
3
K2CO
1
1
1
K
2
CO
2
H O
H2O
0
.15 mol% of the catalyst. There was no reacꢀon when the less
K2CO
reactive aryl chlorides were used (not shown in table) in the
coupling reaction with arylboronic acids, while the reaction
proceeded with adding of 0.5 equiv of TBAB (tetra butyl ammonium
bromide) as a phase transfer catalyst (entries 26‐28).
Len et al. reported that the addition of arylboronic acids to Pd(II) in
K2CO
H2O
60
c
14
K
2
CO
H
2
O
100
1
9
a) 1 mg Cat. = 0.03 mol% Pd for 0.2 mmol arylhalide, b) GC yield
c) 6h
Table 3 The Suzuki‐Miyaura coupling reaction of various aryl halides and boronic acids in the presence of MNP‐CD‐Pd catalyst
MNP-CD-Pd (n mol%)
Ar1 X +
Ar2 B(OH)
Ar1 Ar2
2
K CO (1.5 equiv)
2
3
H O (2 mL), reflux
2
a
Entry
Ar
Ph
Ph
Ph
Ph
Ph
Ph
Ph
1
Ar
Ph
4‐Me‐C
4‐OMe‐C
3‐NO ‐C
3,5‐difluoro‐C
2‐Benzofuranyl
2‐Naphtyl
2,6‐dimethyl‐C
2
X
I
I
I
I
I
I
I
I
I
I
I
I
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cat. (mol%) Time (h)
Yield (%)
Product
3b
3c
3a
3d
3e
3f
3g
3h
3i
1
2
3
4
5
6
7
8
9
0.03
0.03
0.03
0.075
0.03
0.03
0.03
0.15
0.075
0.03
0.075
0.03
0.03
0.03
0.03
0.03
0.06
0.06
0.15
0.075
0.15
0.15
0.075
0.15
0.03
0.3
4
4
4
8
4
6
6
24
8
6
6
4
4
4
4
4
6
6
6
8
8
8
12
8
8
24
24
24
96
100
100
98
99
100 (84)
6
H
4
6
H
4
2
6
H
4
6
H
3
b
b
100 (89)
Ph
Ph
4‐Cl‐C
2‐Me‐C
4‐NO ‐C H
6 4
4‐CHO‐C
Ph
4‐CHO‐C
4‐CHO‐C
Ph
6
H
3
10
99
98
99
98
98
71
100
100
100
84
1‐Naphtyl
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
H
4
Ph
Ph
Ph
Ph
Ph
3j
3k
3l
6
H
4
2
6
H
4
3m
3b
3n
3o
3c
3a
3a
3p
3q
3r
3s
3t
3u
3m
3l
6
6
H
H
4
4‐Me‐C
4‐OMe‐C
4‐Me‐C
6
H
4
4
6
H
4
6
H
4
Ph
4‐OMe‐C
6
H
4
4‐OMe‐C
4‐OMe‐C
4‐OMe‐C
4‐OMe‐C
4‐OMe‐C
4‐OMe‐C
5‐Pyrimidine
4‐CHO‐C
4‐NO
6
H
4
4
4
4
4
4
Ph
96
6
6
6
6
6
H
H
H
H
H
3,5‐difluoro‐C
4‐Me‐C
4‐OMe‐C
6
H
3
98
b
6
H
4
84
b
6
H
4
75
c
b
2‐Benzofuranyl
2‐Naphtyl
Ph
Ph
Ph
Ph
75 (63)
b
83
91
62
65
36
d
2
6
7
8
6
H
4
d
d
2
2
2
‐C
6
H
4
0.3
0.3
Ph
3b
a) GC yield, b) Isolated yield, c) H NMR yield, d) H
2
O/DMF (1:1) as a solvent and 0.5 eq. TBAB
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d
S
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d
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d
a
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Page 6 of 10
Journal Name
ARTICLE
2
1n
water as a solvent afforded Pd(0) species. It is suggested that
Pd(II) in MNP‐CD‐Pd catalyst is reduced in situ in the presence of
arylboronic acids to form catalyꢀcally Pd(0) species on the surface
of MNP‐CD. A proposed mechanism is outlined in Figure 7 for the
Suzuki‐Miyaura coupling reaction of various aryl halides and boronic
acids in the presence of MNP‐CD‐Pd catalyst.
Table
4
w Article Online
optimization of sonogashira couplingViereaction of
iodobenzene and phenylacetylene in the precence MNP‐CD‐Pd
DOI: 10.1039/C6RA04575H
MNP-CD-Pd
(
0.15 mol%)
+
I
base (0.4 mmol)
Solvent (2 mL)
0.24 mmol
0.2 mmol
T
°C)
Time
(h)
6
6
6
6
6
6
6
6
6
6
24
b
Base
Solvent
Yield (%)
(
1
2
3
4
5
6
7
8
9
1
1
K
K
K
2
2
2
CO
CO
CO
3
H
2
O
100
100
100
100
100
100
100
100
100
100
60
43
37
95
52
90
51
74
58
90
96
74
3
H
H
2
O/EtOH (1:1)
O/DMF (3:1)
H2O/DMF (3:1)
O/DMF (3:1)
O/DMF (3:1)
H2O/DMF (3:1)
O/DMF (3:1)
O/DMF (3:1)
H2O/DMF (3:1)
O/DMF (3:1)
3
2
NaOH
Cs CO
Na CO
K3PO4
Et
2
3
H
H
2
2
3
2
3
N
H
H
2
DABCO
K2CO3
2
c
0
1
K
2
CO
3
H
2
a) 1mg Cat. = 0.03 mol% for 0.2 mmol arylhalide, b) GC yield,
c) 0.075 mol% catalyst
catalyst is still stable and organic layers were present on the surface
of the catalyst (Supporting Information).
To the further study on other application of novel prepared
catalyst, we studied the Sonogashira catalytic coupling
reaction of aryl iodides and bromides with terminal alkynes in
Figure 7 Proposed mechanism for the Suzuki‐Miyaura coupling reaction of
various aryl halides and boronic acids in the presence of MNP‐CD‐Pd catalyst the presence of MNP‐CD‐Pd catalyst. In order to obtain
optimized reaction condition, treatment of iodobenzene with
The recyclability and reusability are very important points for phenylacetylene in aqueous solution chosen as the model
heterogeneous catalysis systems. So the reusability of MNP‐CD‐Pd reaction in various reaction conditions. The results are
summarized in Table 4. The results showed that K CO as a
base is a convenient base for Sonogashira coupling reaction of
iodobenzene with phenylacetylene in a solvent mixture of
catalyst in the model reaction (reacꢀon of 4‐bromoanisole with
phenylboronic acid) was investigated. The reusability experiments
results showed that catalytic activity did not decrease considerably
aꢁer four catalyꢀc cycles (Figure 8). Atomic absorpꢀon analysis of
recovered catalyst showed that Pd amount decreased to 0.030
2
3
H O/DMF (3:1) at 100 °C using 0.15 mol% of the catalyst (entry
2
3
). Further invesꢀgaꢀons showed that no decrease in the
reaction yield was observed with decreasing of the catalyst
mmol of pd per gram of MNP‐CD‐Pd after fifth run. The EDS loading to 0.075 mol% (entry 10). So K CO as a base in
2
3
analysis of recycled catalyst confirmed the presence of palladium in
the reused catalyst after fifth run (Figure s14). Thermogravimetric
analysis for recovered MNP‐CD‐Pd after fifth run showed that
2
H O/DMF as solvent in the presence of 0.075 mol% of the
catalyst at 100 °C chosen as opꢀmized reacꢀon condiꢀons.
With having optimized condition, the feasibility of Sonogashira
cross coupling reaction of aryl halides with terminal alkynes in the
presence of MNP‐CD‐Pd catalyst (0.075‐0.15 mol%) was studied
and the results are summarized in Table 5.
As indicated in Table 5, it is observed that the catalyꢀc system is
efficient in the coupling of alkynes with aryl iodides bearing
electron‐donating and electron‐withdrawing functional groups
3
H CO
0.15 mol% cat.
+
OCH
3
B(OH)
2
K
2
CO
6
3
, H
h
2
O
Br
100
(
entries 1‐10). According to the results of table 4 electron‐
withdrawing functional groups in aryl iodide increase reactivity
entries 3 and 4) related to electron‐donating functional groups (
8
0
0
0
0
0
6
4
2
(
entries 8 and 9). Also, reacꢀon of aryl bromides with electron
withdrawing groups proceeded very well and the desired products
were obtained in excellent yields (entries 14 and 16).
1
2
3
4
5
Conclusion
In conclusion, we have developed a new, efficient, greener
Run
1
2
3
4
5
Average
91
and
easily
recoverable
heterogeneous
magnetite
Yield
96
95
97
90
80
nanocatalyst for Suzuki‐Miyaura and Sonogashira carbon‐
carbon coupling reaction in aqueous solution. The
heterogeneous magnetite nanocatalyst for the coupling
reactions is promoted by a novel highly water‐dispersible
magnetite supported palladium‐‐
Figure 8 Reusability test for MNP‐CD‐Pd in the Suzuki–Miyaura coupling
reaction
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 6
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Journal Name
ARTICLE
View Article Online
DOI: 10.1039/C6RA04575H
Table 5 The Sonogashira coupling reaction of various aryl halides and terminal alkynes in the presence of MNP‐CD‐Pd catalyst
MNP-CD-Pd (n mol%)
Ar1 X + Ar2
Ar1
Ar2
K CO (2 equiv)
2
3
o
H O/DMF (2 mL), 100 C
2
a
Entry
Ar
1
Ar
2
X
I
I
I
I
I
I
I
I
Cat. (mol%)
0.075
0.075
0.075
0.075
0.075
0.075
0.075
0.15
Time (h)
Yield (%)
96
Product
6a
6b
6c
6d
6e
6f
1
2
3
4
5
6
7
8
9
Ph
Ph
4‐NO
4‐CN‐C
Ph
4‐Me‐C
Ph
6
3
6
6
6
4
3
6
6
12
9
9
12
6
15
9
6
4
12
6
6
H
4
4
98
2
‐C
6
H
4
100
100
>99
97
96
86
97
96
90
75
85
93
97
95
97
97
82
6
H
4
Ph
Ph
Ph
4‐Cl‐C H
6
4
2‐thiophene
2‐thiophene
4‐Me‐C
Ph
H
6g
4‐OMe‐C
4‐Me‐C H
6
H
4
4
6h
6b
6i
6
Ph
Ph
Ph
Ph
I
I
0.15
0.075
0.15
0.15
0.15
0.15
0.15
0.15
1
1
0
1
2‐Me‐C
6
H
4
4‐CHO‐C
Ph
6
H
4
Br
Br
Br
Br
Br
Br
Br
Br
Br
6j
b
1
1
2
3
6a
6b
6c
6k
6d
6l
b
Ph
4‐Me‐C
6
6
H
4
4
1
4
4‐NO
1‐Naphtyl
4‐CN‐C
2
‐C
6
H
4
Ph
Ph
Ph
Ph
b
15
6
6
H
4
5‐pyrimidine
5‐pyrimidine
0.075
0.075
0.15
4‐Me‐C
Ph
H
6m
6b
b
4‐Me‐C
6
H
4
a
b
2
GC yield, H O/DMF 1:1 and 120 °C
Rev., 2011, 111, 2251‐2320; (n) I. Maluenda, O. Navarro,
Molecules, 2015, 20, 7528‐7557.
cyclodextrin complex that displayed excellent activity for wide
range of substrates in aqueous solution under mild reaction
conditions. The reusability of magnetite supported palladium‐‐
cyclodextrin nanocatalyst was successfully examined five times with
very slight loss of catalytic activity.
2
3
(a) A. F. Littke, G. C. Fu, Angew. Chem. Int. Ed., 2002, 41
4176‐4211; (b) A. Suzuki, J. Organomet. Chem., 2002, 653
,
,
83‐90; (c) A. Suzuki, Angew. Chem. Int. Ed. 2011, 50, 6722‐
6737.
(a) R. Chinchilla, C. Nájera, Chem. Rev., 2007, 107, 874‐922;
(
2
b) P. Li, L. Wang, L. Zhang, G.‐W. Wang, Adv. Synth. Catal.,
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Chaudhary, R. K. Tiwari, A. K. Danodia, Adv. Synth. Catal.,
013, 355, 421‐438; (d) D. Wang, D. Denux, J. Ruiz, D.
Acknowledgment
The authors gratefully acknowledge the support of the Institute for
Advanced Studies in Basic Sciences (IASBS).
2
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RSC Advances
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Table of Contents
A novel highly waterꢀdispersible and recoverable
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magnetite supported palladiumꢀβꢀcyclodextrin complex as
efficient catalyst in SuzukiꢀMiyaura and sonogashira
carbonꢀcarbon coupling reactions
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