KCC-1/GMSI/VB12 as a new nano catalyst for the carbonylative Suzuki-Miyaura crosscoupling reaction

Article abstract of DOI:10.1039/c7ra06021a

In this study, vitamin B12 (VB12) modified with a (3-glycidyloxypropyl)trimethoxysilane (GMSI) moiety grafted onto KCC-1 (KCC-1/GMSI/VB12) was prepared for the first time. Its capability was evaluated for the carbonylative Suzuki-Miyaura crosscoupling reaction between carbon monoxide, 4-iodoanisole and phenylboronic acid, affording the desired products in high yield. Applying 1 mg of catalyst and 1 mmol of K₂CO₃ as base in 10 mL anisole and heating under reflux for 1 h are the best conditions for the reaction. The catalysts were very active in catalytic recycling experiments over ten catalytic cycles.

Full text of DOI:10.1039/c7ra06021a

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KCC-1/GMSI/VB12 as a new nano catalyst for the
carbonylative Suzuki–Miyaura crosscoupling
reaction
Cite this: RSC Adv., 2017, 7, 32139
a
Rahele Zhianiab and Shokufe Emraniab
*
Seyed Mohsen Sadeghzadeh,
In this study, vitamin B12 (VB12) modified with a (3-glycidyloxypropyl)trimethoxysilane (GMSI) moiety
grafted onto KCC-1 (KCC-1/GMSI/VB12) was prepared for the first time. Its capability was evaluated for
the carbonylative Suzuki–Miyaura crosscoupling reaction between carbon monoxide, 4-iodoanisole and
phenylboronic acid, affording the desired products in high yield. Applying 1 mg of catalyst and 1 mmol of
K2CO3 as base in 10 mL anisole and heating under reflux for 1 h are the best conditions for the reaction.
The catalysts were very active in catalytic recycling experiments over ten catalytic cycles.
Received 29th May 2017
Accepted 19th June 2017
DOI: 10.1039/c7ra06021a
rsc.li/rsc-advances
Introduction
The Suzuki coupling reaction has been shown to be an efficient
method for the construction of C–C bonds and plays an
important role in the pharmaceutical industry and organic
synthesis. Biaryl ketones are multipurpose building blocks in
the eld of pharmaceuticals, natural products, agrochemicals
and biologically active compounds.1,2 Among them, the Suzuki
carbonylative coupling reaction is one of the most promising
methods for the direct synthesis of biaryl ketones from carbon
monoxide, aryl halides and arylboronic acids, since a wide
variety of functionalities can be tolerated on either partner and
the arylboronic acids are generally nontoxic and thermally-, air-
and moisture-stable.3–9
The ability of vitamin B12 to catalyse these thermodynami-
cally challenging reactions has attracted the attention of
synthetic chemists. Vitamin B12 is as an environmentally
benign catalyst in organic reactions, which has eventually led to
the discovery of new catalytic transformations. Vitamin B12 is
as a catalyst which need costly and difficult separation of the
catalyst from homogeneous reaction mixtures. For solving this
problem, the use of heterogeneous vitamin B12 is important
advantages in organic synthesis, such as operational simplicity,
reusability, non-toxicity, environmental adaptability, and ease
of isolation. The use of recyclable strong heterogeneous vitamin
B12 in organic reactions are oen considered to follow the
principles of green chemistry, such as operational simplicity,
reusability, non-toxicity, environmental adaptability, and ease
of isolation. Recently, Vivek Polshettiwar reported the synthesis
of new brous silica nanosphere (KCC-1) with high surface area,
Scheme 1 Carbonylative Suzuki–Miyaura coupling.
large open pore structure, and high thermal and hydrothermal
stabilities.10 Therefore, most of its surface area is accessible,
yielding unusually high activity in catalysis.11–25 The KCC-1 is
extremely favorable in the design of the inorganic–organic
hybrid sensing materials owing to the unique physical proper-
ties such as easily accessible of active sites, large open pore
structure, excellent solvent dispersibility, favorable biocompat-
ibility, high surface area, and superparamagnetism. Herein, we
present a facile synthesis of KCC-1 based nanoparticles and was
further functionalized by a vitamin B12 with (3-glycidylox-
ypropyl)trimethoxysilane (GMSI) linker that have been applied
as novel nano catalyst for the carbonylative Suzuki–Miyaura
crosscoupling reaction (Scheme 1).
Experimental
Materials and methods
Chemical materials were purchased from Fluka and Merck in
high purity. Melting points were determined in open capillaries
using an Electrothermal 9100 apparatus and are uncorrected.
FTIR spectra were recorded on a VERTEX 70 spectrometer
(Bruker) in the transmission mode in spectroscopic grade KBr
pellets for all the powders. The particle size and structure of
nano particle was observed by using a Philips CM10 trans-
mission electron microscope operating at 100 kV. Powder X-ray
diffraction data were obtained using Bruker D8 Advance model
with Cu Ka radiation. The thermogravimetric analysis (TGA)
aDepartment of Chemistry, Faculty of Sciences, Neyshabur Branch, Islamic Azad
University, Neyshabur, Iran. E-mail: seyedmohsen.sadeghzadeh@gmail.com
bYoung Researchers and Elite Club, Neyshabur Branch, Islamic Azad University,
Neyshabur, Iran
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was carried out on a NETZSCH STA449F3 at a heating rate of monitored by TLC when the reaction was completed, EtOH was
10 ꢀC minꢁ1 under nitrogen. 1H and 13C NMR spectra were added to the reaction mixture and the catalyst was separated by
recorded on a BRUKER DRX-300 AVANCE spectrometer at an external magnet. Then the solvent was removed from solu-
300.13 and 75.46 MHz, BRUKER DRX-400 AVANCE spectrom- tion under reduced pressure and the resulting product puried
eter at 400.22 and 100.63 MHz, respectively. Elemental analyses by recrystallization using n-hexane/ethyl acetate.
for C, H, and N were performed using a Heraeus CHN–O-Rapid
analyzer. The purity determination of the products and reaction
monitoring were accomplished by TLC on silica gel polygram
SILG/UV 254 plates. Mass spectra were recorded on Shimadzu
Results and discussion
In this study, we have investigated the effect of KCC-1/GMSI/
VB12 NPs catalyst on the carbonylative Suzuki coupling reac-
tion of iodobenzene with phenyl boronic acid. The VB12 func-
tional groups in KCC-1/GMSI as a dendrimer could strongly
favour the loading of VB12 due to the interaction between OH
groups of VB12 and the internal epoxide groups of the den-
drimer is believed to be the main reason for the loading of VB12
inside the dendrimer (Scheme 2).
GCMS-QP5050 Mass Spectrometer.
General procedure for the preparation of KCC-1 nanoparticles
In order to synthesize KCC-1, at rst cetyltrimethyl ammonium
bromide (CTAB 1 g, 0.0027 mol) and urea (0.6 g, 0.01 mol) was
dissolved in deionized water. This solution was stirred for about
3 h until all of CTAB was dissolved. Then this solution was
added to solution of tetraethyl orthosilicate (TEOS, 2.5 g, 0.012
mol), cyclohexane (30 mL), and pentanol (1.5 mL). This mixture
was stirred for 30 min at room temperature, and the resulting
solution was reuxed at 120 ꢀC under stirring in oil bath for 4 h.
This solution placed in oven at 80 ꢀC for 24 h. Then the mixture
was allowed to cool to room temperature and the silica formed
was isolated by centrifugation (30 min, 6000 rpm), then washed
with deionized water and acetone repeatedly and air-dried for
ꢀ
24 h. The as-synthesized material was then calcined at 550 C
for six hours in air.
General procedure for the preparation of KCC-1/GMSI NPs
KCC-1 (2 mmol) and THF (20 mL) were mixed together in
a beaker, and then NaH (20 mmol) was dispersed in to the
mixture by ultrasonication. (3-Glycidyloxypropyl)trimethox-
ysilane (GMSI) (22 mmol) was added drop-wise at room
temperature and stirred for another 16 h at 60 ꢀC. The resultant
products were collected and washed with ethanol and deionized
water in sequence, and then dried under vacuum at 60 ꢀC for 2 h
for further use.
General procedure for the preparation of KCC-1/GMSI/VB12
NPs
Scheme 2 Schematic illustration of the synthesis for KCC-1/GMSI/
VB12 NPs.
KCC-1/GMSI (1 g), VB1 (1.5 mmol), and DMF (50 mL) were
mixed together with magnetic stirrer bar. The reaction mixture
ꢀ
was stirred for 5 h at 60 C and was subsequently ltered and
washed thoroughly with DMF, dried in oven at 60 ꢀC for 24 h to
form the KCC-1/GMSI/VB12 NPs.
General procedures for preparation of the carbonylative
Suzuki reaction of aryl iodides
To a 100 mL autoclave, aryl iodide (1.0 mmol), aryl boronic acid
(1.2 mmol), KCC-1/GMSI/VB12 (1 mg), anisole (10 mL) and
K2CO3 (3 mmol) were added. The autoclave was closed, purged
twice with CO gas, pressurized with 1 MPa of CO and then
heated under reux for 1 h. Aer completion of the reaction, the
reaction mixture was cooled to room temperature and the
remaining CO gas was carefully vented and the reactor was
Fig. 1 SEM image of the fresh KCC-1/GMSI/VB12 NPs (a), and SEM
opened. Upon completion, the progress of the reaction was images of KCC-1/GMSI/VB12 NPs after ten reuses (b).
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Table 1 Chemical composition of the reaction components using ICP
Entry
Element
Weight percent (%)
1
2
3
4
5
6
Pd
Cu
Fe
Ni
Cd
Co
—
<0.01
<0.01
—
<0.01
—
surface, respectively (Fig. 2b). FTIR spectrum of cobalamin is
shown as a reference. The spectrum of VB12 shows two major
parts. The broad peak at about 3400 cmꢁ1 is assigned to the
O–H stretching of the hydroxyl groups attached to the surface.26
The second peak is in around of 1665 cmꢁ1. The C]O
stretching vibration due to propionamide side chain of VB12
caused the appearance of this intense peak at 1670 cmꢁ1
(Fig. 2a).27–29 Peak appeared at 3390 cmꢁ1, 3120 cmꢁ1, 2930
cmꢁ1, and 1665 cmꢁ1 are due to the stretching of the hydroxyl
group (–OH), the C–H aromatic group, the C–H aliphatic group,
and C]O group in the KCC-1/GMSI/VB12 NPs (Fig. 2c). By
comparing the three parts of Fig. 2, the formation of a new band
at 751 cmꢁ1 is evident. Although, this peak is situated in the
ngerprint region of the IR spectrum, a new event is detected
aer the VB12 loading process, whereas no such peak is
observed in the pristine VB12 and KCC-1 spectra. This
phenomenon can be an evidence for the conjugation of VB12
molecules to KCC-1 NPs.
The TG analysis of KCC-1/GMSI/VB12 NPs was determined
and shown in Fig. 3. A signicant decrease in the weight
percentage of the KCC-1/GMSI/VB12 NPs at about 130 ꢀC is
related to desorption of water molecules from the catalyst
surface. This was evaluated to be 1–3% according to the TG
analysis. In addition, the analysis showed two other decreasing
peaks. First peak appears at temperature around 250–280 ꢀC
due to the decomposition of Co. This is followed by a second
peak at 420–460 ꢀC, corresponding to the loss of the organic
spacer group. The major concern is related with a plausible
presence of trace amounts of other active metal (like Pd, Cu, Fe,
Ni, Cd, and Co) in any component of the reaction. To solve this
problem it was necessary to carry out an ICP analysis of the
reaction components. You can see in Table 1 that the concen-
tration of Pd, Cu, Fe, Ni, Cd, and Co were very low that discard
the slightest doubt.
Fig. 2 FTIR spectra of vitamin B12 (a); KCC-1 (b); and KCC-1/GMSI/
VB12 NPs (c).
The SEM images of the KCC-1/GMSI/VB1 NPs catalysts were
shown in Fig. 1. As can be seen from the Fig. 1a, the KCC-1/
GMSI/VB1 NPs had a consistent particle size range of 260–
380 nm. SEM image shown in Fig. 1a further claries that the
distance between the two bers was about 10–15 nm. The
recyclability test was stopped aer ten runs. Comparison of
SEM images of used catalyst (Fig. 1b) with those of the fresh
catalyst (Fig. 1a) showed that the morphology and structure of
KCC-1/GMSI/VB1 NPs remained intact aer ten recoveries.
Agglomeration of KCC-1/GMSI/VB1 NPs can not be seen.
FT-IR spectroscopy was employed to determine the surface
modication of the synthesized catalyst (Fig. 2). The bands at
802, 1103 and 1630 cmꢁ1 observed in the FT-IR spectra of both
KCC-1 is related to the typical silanol group (Si–OH) stretching
mode, Si–O–Si vibrations and the water absorbed on the solid
To optimize the reaction conditions, the carbonylative cross-
coupling reaction of iodobenzene with phenyl boronic acid in
the presence of KCC-1/GMSI/VB12 as a catalyst was chosen as
a model system. The inuence of various parameters such as
solvent, base, and time (Table 2) were examined on the model
reaction. The inuence of solvents on the carbonylative Suzuki
coupling reaction was investigated (Table 2, entries 1–15).
According to the evaluated results of solvents, when polar protic
solvents, such as methanol, isopropanol, ethanol, and water,
were showed that any amount of the desired product was not
formed. However, the yield of the cross-coupling product was
Fig. 3 TGA diagram of KCC-1/GMSI/VB12 NPs.
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Table 2 Carbonylative Suzuki–Miyaura reaction by KCC-1/GMSI/VB12
NPs in different solvents, bases, and timea
Entry
Solvent
Base
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
8
EtOH
H2O
CH3CN
DMF
CH2Cl2
EtOAc
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
—
CsF
Na2CO3
Et3N
NaOAc
KOH
K3PO4
Cs2CO3
tBuOK
K2CO3
K2CO3
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1
—
—
46
59
38
21
32
63
—
32
41
—
—
—
96
—
—
—
62
—
—
43
70
67
—
96
90
THF
Toluene
n-Hexane
CHCl3
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
DMSO
Fig. 5 Effect of pressure on yield of carbonylative Suzuki–Miyaura
reaction.
MeOH
Dioxane
i-PrOH
Anisole
Solvent-free
Anisole
Anisole
Anisole
Anisole
Anisole
Anisole
Anisole
Anisole
Anisole
Anisole
Anisole
that conventional heating under anisole is more efficient than
using organic solvents (Table 2, entries 8). It is well known that
bases play a crucial role in coupling reactions; hence we
attempted the reaction in the presence of various organic and
inorganic bases (Table 2, entries 16–26). As a result, the most
used base K2CO3 was the most efficient base to produce car-
bonylative cross-coupling product. Under the optimal condi-
tions, the reaction progress for the shortest time necessary in
the presence of 2 mg of KCC-1/GMSI/VB12 NP was monitored by
GC, that excellent yields of carbonylative Suzuki coupling
reaction can be achieved in 1 h (Table 2, entries 26).
0.5
a
Reaction conditions: iodobenzene (1 mmol), phenyl boronic acid (1.2
mmol), KCC-1/GMSI/VB12 NPs (1 mg), K2CO3 (3 mmol), solvent (10 mL),
CO pressure ¼ 3 MPa. b Isolated yields.
We also study the decisive role of temperature in the
synthesis of carbonylative Suzuki–Miyaura reaction in the
presence of KCC-1/GMSI/VB12 NPs as a catalyst. The best
temperature for this reaction heating under reux do cause
changes in the efficiency of the reaction, that showed the
catalytic activity is susceptible to reaction temperature. The
catalyst loading is another important factor in current reac-
tion for the carbonylative cross-coupling reaction (Fig. 4). As
shown in Fig. 4, the low yield of carbonylative Suzuki–Miyaura
reaction was gained when model reaction was performed in
the absence of a catalyst. When 0.2–0.8 mg of KCC-1/GMSI/
VB12 NPs were elaborated on sample reaction, moderate
yields of carbonylative Suzuki coupling reaction were ob-
tained. The best result was achieved when the model reaction
was carried out in the presence of 1 mg of KCC-1/GMSI/VB12
NPs. A rise in the catalyst amount showed no upgrading in the
model reaction. In the absence of the catalyst no product was
obtained. Effects of CO pressure in the presence of iodo-
benzene, phenyl boronic acid, and KCC-1/GMSI/VB12 NPs for
1 h was shown in Fig. 5. The catalyst mixture reaches an
average of >96% of conversion at 1 MPa pressure. No apparent
by-products were observed by GC in all the experiments and
carbonylative Suzuki–Miyaura reaction was obtained cleanly
in 96% yield.
relatively average in polar aprotic solvents, such as DMF,
CH2Cl2, EtOAc, CHCl3, anisole, and DMSO. When the reaction
was conducted in less polar solvents, such as anisole or toluene,
good to high yields of carbonylative cross-coupling product
were isolated, and anisole was found to be the best choice.
However, the carbonylative cross-coupling product was ob-
tained in low yield in polar solvents. In this study, it was found
With the optimized reaction conditions, we extended the
scope of carbonylative Suzuki reaction to a variety of different
aryl iodides with phenyl boronic acids. As shown in Table 3,
various electron-donating and electron-withdrawing groups
Fig. 4 Effect of increasing amount of KCC-1/GMSI/VB12 NPs on the
preparation of vitamin K3.
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Table 3 Carbonylative Suzuki coupling reaction of various aryl iodides
with appreciable yields. Iodobenzene reacted with phenyl
boronic acid giving 96% yield of benzophenone (Table 3, entry
1). It is worth noting that aryl iodides containing electron-
withdrawing groups, such as –Br, –Cl, –COCH3 and –NO2,
were found to be the more active than aryl iodides containing
electron-donating groups, such as –CH3, –OCH3 and –NH2.
For further investigation the efficiency of the catalyst,
different control experiments were performed and the ob-
tained information is shown in Table 4. Initially, a standard
reaction was carried out using KCC-1 showed that any amount
of the desired product was not formed aer 1 h of reaction
time (Table 4, entry 1). Also, when KCC-1/GMSI was used as the
catalyst, a reaction was not observed (Table 4, entry 2). The
GMSI could not give the satisfactory catalytic activity under
mild reactions. We compared the results achieved in this work
with elsewhere over many other similar catalysts. In contrast
with the catalysts of VB12 as a homogeneous catalysis our
catalyst requires similar condition for the carbonylative cross-
coupling (Table 4, entries 3 and 5). Also, the activity and
selectivity of nano-catalyst can be manipulated by tailoring
chemical and physical properties like size, shape, composition
and morphology. To assess the exact impact of the presence of
KCC-1 in the catalyst, the KCC-1/GMSI/VB12 NPs compared
with SiO2/GMSI/VB12 NPs. To check this, we looked at SiO2/
GMSI/VB12 and KCC-1/GMSI/VB12 NPs, which have the same
compositions and different structures. When SiO2/GMSI/VB12
was used as the catalyst, the yield of the desired product was
fair to average, but the yield for KCC-1/GMSI/VB12 was good
(Table 4, entries 3 and 4).
with arylboronic acid in the presence of the KCC-1/GMSI/VB12 NPsa
Entry
1
Aryl iodide
Product
Yieldb (%)
96
2
3
4
5
92
90
98
97
6
7
86
83
We compared the catalytic performance of our catalyst with
catalysts reported for carbonylative Suzuki coupling reaction
(Table 5). Table 5 clearly demonstrates that the most favourable
terms are required for carbonylative Suzuki coupling reaction,
using KCC-1/GMSI/VB12 NPs, while an appropriate, highly
perfect, performance of the present catalyst is observed for the
reaction.
8
85
a
Reaction condition: iodobenzene (1 mmol), phenyl boronic acid (1.2
mmol), KCC-1/GMSI/VB12 NPs (1 mg), K2CO3 (3 mmol), solvent (10
mL), CO pressure 1 MPa aer 1 hour. b Yield refers to isolated product.
To obtain information about the heterogeneity or homogeneity
of the catalytic reaction, hot ltration and mercury poisoning tests
were carried out. At rst, the relationship between the progress of
reaction and time was maximum at the range of 3–6 h. Thus, we
chose the point of 5 h for the following experiments. The catalyst
such as –CH3, –OCH3, –NH2, –COCH3, –NO2, –Br and –Cl on
both aryl iodide and aryl boronic acid smoothly underwent
carbonylative Suzuki coupling reaction giving desired products
ꢀ
was ltered out at above 100 C aer the reaction proceeded for
6 h and the yield of benzophenone was 74% determined by GC.
The obtained ltrate with additional 1.0 mmol phenyl boronic
acid was continually stirred under the reaction conditions. Aer 6
hours the conversion was determined to be 74%. The same
approach was applied to mercury test. Aer the rst stage, the
yield of benzophenone was 72%. In the second stage, aer
mercury (0.3 mL) was added into the ltrate, the ltrate was
stirred for another six hours under the reaction conditions. The
yield of benzophenone remained to be 74%. These phenomena
show that a small amount of catalytically active VB12 species may
have leached to the reaction mixture (Fig. 6). But the contents of
VB12 in catalyst before and aer reaction were 5.7% and 5.5%
respectively, determined by ICP-MS. These indicate that most of
VB12 species leaching into solution are recaptured onto the bers
of KCC-1 aer completion of the reaction (Table 6). It is important
Table
4 Influence of different catalysts for carbonylative Suzuki
coupling reactiona
Entry
Catalyst
Catalyst loading
Yieldb (%)
1
2
3
4
5
KCC-1
1 mg
1 mg
1 mol%
1 mol%
1 mol%
—
—
96
59
97
KCC-1/GMSI
KCC-1/GMSI/VB12
SiO2/GMSI/VB12
VB12
a
Reaction conditions: iodobenzene (1 mmol), phenyl boronic acid (1.2
mmol), K2CO3 (3 mmol), solvent (10 mL), CO pressure 1 MPa aer 1
hour. b Isolated yield.
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Table 5 Comparison of the catalytic efficiency of KCC-1/GMSI/VB12 NPs with various catalystsa
Entry
Catalyst
Experimental conditions
Yield (%)
Ref.
1
2
3
4
5
6
7
Pd/C
100 ꢀC, 8 h, 4 bar CO
120 ꢀC, 12 h, 30 bar CO
80 ꢀC, 8 h, 1 bar CO
100 ꢀC, 10 h, 7 bar CO
80 ꢀC, 9 h, 1 bar CO
80 ꢀC, 8 h, 1 bar CO
Reux, 1 h, 1 bar CO
90
86
91
94
94
91
96
30
31
32
33
34
35
P(DVB-NDIIL)-Pd
Fe3O4@SiO2-2N-Pd
PS-Pd-NHC
HMMS-SH-Pd
MCM-41-2N-Pd
KCC-1/GMSI/VB12
This work
a
Reaction conditions: iodobenzene (1.0 mmol), phenylboronic acid (1.2 mmol), in different temperature, time, and pressure of CO.
Conclusions
In summary, a novel class of short-ber KCC-1 mesoporous
silica functionalized with 1,3-bis(dimethylthiocarbamoyloxy)
benzene groups ligands was synthesized for selective capturing
of VB12, that exhibited excellent catalytic activity for carbon-
ylative Suzuki coupling reaction in good yields. FTIR, SEM, TGA,
ICP-MS, and BET surface area analysis studies suggested the
functionalization of VB12 in the surface of the mesopores silica.
In addition, the catalyst was easily recoverable and reusable.
Such a rational design for single-site catalysts with full utiliza-
tion of each VB12 active site, as well as excellent recyclability
and negligible catalyst leaching could coincide with the
concepts of green chemistry. Thus, the study of KCC-1/GMSI/
VB12 nanocatalyst may provide a potential platform for the
fabrication of other nano catalyst with easy accessibility, which
would be highly efficient in various nano catalyst based catalytic
reactions. This process may be used in the future to develop
additional nanocatalysts that possess favorable properties, such
as efficiency and ease of reuse.
Fig.
reaction.
6 Effect of time on yield of carbonylative Suzuki coupling
Table 6 The loading amount of VB12 in KCC-1/GMSI/VB12 NPs
Entry
Catalyst
wt%
1
2
KCC-1/GMSI/VB12 NPs
KCC-1/GMSI/VB12 NPs aer ten reuses
5.7
5.5
Notes and references
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