Insight into the catalytic properties and applications of metal-organic frameworks in the cyanosilylation of aldehydes

Article abstract of DOI:10.1039/c5ra13102b

Here we present a systematic investigation of the cyanosilylation of aldehydes with trimethylsilyl cyanide (TMSCN) by using metal-organic frameworks (MOFs) as catalysts. Four types of thermally stable MOFs (MIL-47 (V), MIL-53 (Al), MIL-101 (Cr), and UiO-6

Full text of DOI:10.1039/c5ra13102b

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Insight into the Catalytic Properties and Applications of Metal-
Organic Frameworks in the Cyanosilylation of Aldehydes
Received 00th January 20xx,
Accepted 00th January 20xx
Zhiguo Zhang, Jingwen Chen, Zongbi Bao, Ganggang Chang, Huabin Xing and Qilong Ren*
Here we present a systematic investigation of the cyanosilylation of aldehydes with trimethylsilyl cyanide (TMSCN) by
using metal-organic frameworks (MOFs) as the catalysts. Four types of thermal stable MOFs (MIL-47 (V), MIL-53 (Al), MIL-
101 (Cr), and UiO-66 (Zr)) constructed with the same organic linker, terephthalic acid, were studied, among which MIL-101
(Cr) exhibits the highest catalytic activity. Experimental results revealed that the catalytic activities are in close relation
with the types of coordinatively unsaturated metal ions, pore sizes as well as solvents. Using MIL-101 (Cr) as the catalyst,
both aliphatic and aromatic aldehydes were efficiently transformed to cyanohydrin trimethylsilyl ether, meanwhile
significant size selectivities and electronic effects have also been observed. The solvent-free reaction conditions not only
provide a high TON for MOF catalyzed cyanosilylation, but also render current protocol more attractive to industrial
applications.
DOI: 10.1039/x0xx00000x
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pore sizes and diverse functionalizations have pointed toward
their potential utility to be size- and shape-selective
heterogeneous catalysts.7 The vacant coordination sites in
Introduction
Cyanohydrins play an important role in chemistry and biology.
They are widely employed as versatile building blocks for fine
chemicals, agrochemicals and pharmaceuticals, i.e. α-hydroxy
acids, β-amino alcohols, etc.1 Generally, the addition of
cyanide to carbonyl compounds represents one of the
fundamental approaches for their preparation and has
frequently been at the forefront of synthetic chemistry.2 In
consideration of easy and safe management, the most often
used cyanide source is trimethylsilyl cyanide (TMSCN), which
allows the cyanohydrins to be prepared as the corresponding
trimethylsilyl ether.2b,3
MOFs can activate carbonyl compounds for nucleophilic
addition in a manner similar to Lewis acids. Since the first
example of MOFs catalyzed reaction was reported by Fujita et
al.,8 dozens of papers concerning MOF-based heterogeneous
catalysis have been thus far published.9 More specifically,
Kaskel and co-workers10 demonstrated that pure MIL-101 (Cr)
is an efficient catalyst for the cyanosilylation of benzaldehyde.
Recently, Corma and coworkers11 selected several MOFs to
catalyze the cyanosilylation of benzaldehyde with TMSCN, in
which they demonstrated the differences in the catalytic
performance of MOFs with their homogeneous counterparts
and other conventional solid catalysts.
In the past several decades, a variety of activators or
promoters have been reported for this transformation.1a,1c,2b,3-
4
Interestingly, despite the progress on MOFs catalyzed
reactions, there has been little focus on the investigation of
reaction mechanisms and subsequent improvement of their
catalytic performance. As part of our efforts to develop
practically effective catalysts for cyanosilylations,5a we turned
our attention to several typical MOFs with diverse structures
and topologies by presenting their potential and limitations
using cyanosilylation of aldehydes as a probe reaction. Herein,
we report our preliminary results by means of a systematic
study on kinetic profile, Lewis acidity effect, solvent effect, and
substrate scope, etc.
In light of environmental benign pressures, organocatalysts
have grown rapidly in promoting the cyanosilylation of
carbonyl compounds with TMSCN.5 Although organocatalytic
systems comply with some features of green chemistry, they
are still encountered with tedious separation and recycle
problems in practical applications. Therefore, a mild, efficient
and environmental friendly synthetic method for cyanohydrin
trimethylsilyl ethers is still highly desirable.
Metal-organic frameworks (MOFs) are a new generation of
materials, which were constructed via the coordination of
organic ligands with metal clusters.6 The unique properties of
MOFs, such as porosity, high specific surface area, tunable
Experimental
General information
All chemicals were of reagent grade, obtained from
commercial sources and used without further purification
unless otherwise stated. The benzaldehyde was freshly
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distilled before use and the solvents were dried by standard
methods prior to use.
The FT-IR spectra were recorded on a Nicolet 6700 FT-IR
spectrometer in the range of 400-4000 cm-1 by using
potassium bromide pellets. 1H NMR spectra were measured on
a Bruker 400 MHz NMR spectrometer. The catalytic results
were monitored by
a gas chromatography (GC) on an
SHIMADZU GC2010 Plus. Nitrogen adsorption and desorption
isotherms were measured on a 3Flex instrument. The powder
X-ray diffraction (XRD) pattern of MIL-101 (Cr) was obtained on
a SHIMADZU XRD-6000 diffractometer with Cu Kα radiation.
Following conditions were used: 40 kV, 40 mA, scan speed = 4
deg/min, increment = 0.02°.
Synthesis and Characterization of MOFs
MIL-47 (V),12 MIL-53 (Al),13 MIL-101 (Cr)14 and UiO-66 (Zr)15
were synthesized and purified according to the methods
described in literature (see ESI†).
Fig. 1 The crystal structures of (a) MIL-47 (V), (b) MIL-53 (Al), (c) MIL-101 (Cr), and (d)
UiO-66 (Zr). Grey, red and white balls or sticks represent carbon, oxygen and hydrogen
atoms, respectively. Vanadium octahedron in (a), aluminum octahedron in (b),
chromium octahedron in (c) and zirconium octahedron in (d) are in blue, rose red,
green and orange, respectively. Hydrogen atoms in the framework are omitted for
clarity.
General procedure for cyanosilylation reactions
All kinds of MOFs were treated at 150 °C for 12 h previously to
get solvent free catalysts. In
a typical cyanosilylation
procedure, the activated MOF was introduced into a mixture
of TMSCN (1.2 mmol) and aldehyde (1.0 mmol). The reaction
mixture was stirred vigorously at room temperature. The
conversion of aldehyde was determined by gas
chromatography at a given time interval by using tridecane as
2, MIL-53 (Al) (Table 2, entry 2) had a least influence on
ν(C=O),indicating the weak interaction between benzaldehyde
and MIL-53 (Al), which consequently resulted in lowest
catalytic activity. The effect of MIL-47 (V) (Table 2, entry 1) on
ν(C=O) is medium, and MIL-101 (Cr) (Table 2, entry 3) and UiO-
66 (Zr) (Table 2, entry 4) had a strong influence on ν(C=O). So,
the interaction strength of benzaldehyde with the framework
is in the following sequence: UiO-66 (Zr) ≈ MIL-101 (Cr) > MIL-
47 (V) > MIL-53 (Al).
1
the internal standard. The yields were determined by H NMR
analysis. The mol percent amount of catalyst was refers to the
whole formula of MOFs.
Results and discussion
Catalytic properties
The larger low-frequency shift of ν(C=O) in MIL-101 (Cr) and
UiO-66 (Zr) absorbed benzaldehyde, indicating the strong
interaction between the metal centres and the carbonyl
oxygen atoms. From another point of view, it should be noted
The cyanosilylation reaction between TMSCN and
benzaldehyde was chosen as the model reaction system to
assess the catalytic properties of four MOFs, including MIL-47
(V), MIL-53 (Al), MIL-101 (Cr) and UiO-66 (Zr) (Fig. 1). As
showed in Table 1, the reaction without catalyst (Table 1, entry
5) resulting only 19% conversion of benzaldehyde. However, in
the presence of 1.0 mol% of catalyst, we are pleased to find
that all MOFs can accelerate this reaction under solvent free
conditions and MIL-101 (Cr) (Table 1, entry 3) gives the highest
conversion at the same time intervals.
Table 1 Comparison of MOFs catalyzed cyanosilylation of benzaldehyde.a
O
OTMS
CN
MOF (1.0 mol%)
neat, rt
H
+
TMSCN
Since these MOFs are constructed by the same organic
linker but with different metal clusters, we had initially
hypothesized that the reaction rate is mainly related with the
nature of metal ions in the catalysts. The coordinatively
unsaturated metal ions can act as Lewis acid sites and
coordinate with the carbonyls. In order to obtain experimental
evidences for such interactions, we applied FT-IR spectroscopic
method using benzaldehyde as a probe molecule.16 After
comparison of the frequency shift between pure benzaldehyde
and the MOFs absorbed benzaldehyde in FT-IR spectrum, we
found that all the C=O stretching vibrations of the absorbed
Entry Catalyst
Formula
Time (h)
Conv.b (%)
1
2
MIL-47 (V)
VIVO[O2C-C6H4-CO2]
Al(OH) [O2C-C6H4-CO2]
Cr3XO[O2C-C6H4-CO2]3
(X=F/OH)
3
3
46
26
MIL-53 (Al)
3
MIL-101 (Cr)
3
96
4
5
UiO-66 (Zr)
none
Zr6O4(OH)4(CO2)12
-
3
3
68
19
a
Conditions: benzaldehyde (1.0 mmol), TMSCN (1.2 mmol), catalyst (1.0
mol%), rt, 3 h.
b The conversion of benzaldehyde was determined by GC analysis using tridecane
benzaldehyde are shifted to low-frequency. As shown in Table as the internal standard.
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Table 2 FT-IR spectroscopic studies on the interaction of benzaldehyde with MOFs.
Table 3 MIL-101 (Cr) catalyzed cyanosilylation of benzaldehyde in various solvents.a
Entry
MOFs
ν(C=O)/cm-1
1693.2
△ν(C=O)a/cm-1
O
OTMS
CN
1
2
3
4
MIL-47 (V)
MIL-53 (Al)
MIL-101 (Cr)
UiO-66 (Zr)
10.4
6.3
MIL-101 (Cr) (0.3 mol%)
solvent, rt
H
1697.3
+
TMSCN
1689.5
14.1
15.2
1688.4
Entry
Solvent
Conv.b (%)
a
Calculated by subtracting the carbonyl stretching vibration frequency of the
observed value from that of the pure benzaldehyde (1703.6 cm-1).
1
2
3
4
5
Solvent free
Heptane
96
87
9c
Acetonitrile
Dichloromethane
Tetrahydrofuran
11
that, the pore size (30 to 40 Å)14b inside the framework of MIL-
101 (Cr) is the largest amongst these four MOFs, which allows
the easy diffusion and permeability of substrates to the
exposed metal sites within the pores; while accessing to the
internal surface of UiO-66 (Zr) is restricted by triangular
windows with opening of 6 Å.15 Therefore, given that MIL-101 standard.
(Cr) and UiO-66 (Zr) have similar influence on ν(C=O), they
trace
a Reaction conditions: benzaldehyde (1.0 mmol), TMSCN (1.2 mmol), catalyst (0.3
mol%), solvent (3 mL), rt, 4 h.
b
The conversion was determined by GC analysis using tridecane as the internal
c Using o-xylene as the internal standard for GC analysis.
showed different catalytic activities (Table 1, entry 3-4).
Similarly, the low catalytic activities of MIL-47 (V) and MIL-53
(Al) might also be affected by their respective small pore sizes
(10.5 × 11.0 Å and 8.5 × 8.5Å).12-13 Furthermore, the deficiency
of active Lewis acidic sites within MIL-47 (V) and MIL-53 (Al) is
probably the main restriction on the catalytic performance.
This study suggested that both active Lewis acid sites and pore
sizes are crucial to the MOF catalyzed cyanosilylation. Taking
advantage of both the biggest pore size and the strongest
Lewis acidity among MOFs tested, MIL-101 (Cr) was selected to
be the catalyst for further studies on cyanosilylation reaction.
With the optimal catalyst in hand, we then focused on
optimizing the reaction conditions. First, different loadings of
MIL-101 (Cr), 1.00 mol%, 0.55 mol%, 0.30 mol%, 0.25 mol%
and 0.15 mol%, were employed to catalyze the cyanosilylation
reaction of benzaldehyde. The reactions were carried out
under the following conditions: 1.0 mmol of benzaldehyde, 1.2
mmol of TMSCN, and the chosen amount of MIL-101 (Cr), and
the resulting mixture was stirred vigorously at room
temperature under solvent free conditions. Aliquot of the
reaction mixture was taken out to be analyzed by GC to
measure the conversion of benzaldehyde. The conversion of
benzaldehyde vs. time was plotted in Fig. 2. The catalyst
loading of MIL-101 (Cr) can be reduced to 0.3 mol% without
obvious influence on reaction outcome. In addition, 0.15 mol%
of MIL-101 (Cr) is still sufficient to activate this transformation
albeit at the expense of somewhat time elongation. Finally, 0.3
mol% of MIL-101 (Cr) was chosen for further studies (Table S1,
ESI†).
Solvent effect
In order to investigate the role of solvents in the
cyanosilylation reaction, the additions of TMSCN to
benzaldehyde were carried out in different solvents. As seen in
Table 3, in contrast to 96% conversion within 4 hours under
solvent free condition (Table 3, entry 1), the rate of the
reaction was found to decrease when heptane was added
(Table 3, entry 2). Furthermore, much lower conversion was
observed when the reaction was performed in CH3CN (Table 3,
entry 3) or CH2Cl2 (Table 3, entry 4) probably due to
competitive coordination of Cr with negatively charged atoms
in solvents. Finally, THF (Table 3, entry 5) can completely
inhibit the reaction to occur by its strong coordination ability
to unsaturated Cr sites and shut down the active Lewis acid
sites. Therefore, solvent free conditions proved to be superior
to those performed in conventional solvents. Hence, this
reaction condition was further applied to other aldehydes.
100
80
Substrate scope
1.00 mol% of MIL-101 (Cr)
60
Using 0.3 mol% of MIL-101 (Cr) as the catalyst under solvent
free conditions, we next explore the generality of MIL-101 (Cr)
for the cyanosilylation of various aldehydes. As indicated in
Table 4, both aliphatic (Table 4, entry 1-3) and aromatic
aldehydes (Table 4, entry 4-16) are well tolerated with this
reaction protocol and could be converted to the corresponding
O-trimethylsilyl cyanohydrin in good yields. Aliphatic
aldehydes (Table 4, entry 1-3) and benzaldehydes bearing
electron-withdrawing groups on aromatic rings (Table 4, entry
5-10) proceed smoothly to give the respective cyanosilylation
0.55 mol% of MIL-101 (Cr)
0.30 mol% of MIL-101 (Cr)
0.25 mol% of MIL-101 (Cr)
0.15 mol% of MIL-101 (Cr)
40
20
0
0
2
4
6
8
Time (h)
Fig. 2 Kinetic profiles for the cyanosilylation of benzaldehyde catalyzed by different
amounts of MIL-101 (Cr).
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products with high yields. Benzaldehydes bearing electron- the above results, MIL-101 (Cr) demonstrated its size
donating groups (Table 4, entry 11-12) react much more slowly selectivity and applicable substrate dimensions.
than benzaldehydes with electron-withdrawing groups. The
It is worthy of noting that the TON of the cyanosilylation of
electronic effects are more significant for para-substituted benzaldehyde catalyzed by MIL-101 (Cr) under solvent free
substrates, as the yield of 3-methoxybenzaldehyde (Table 4, condition is 320 (refers to metal ions), which exhibits high
entry 11) is much higher than that of p-anisaldehyde (Table 4, catalytic performance in comparison to those protocols
entry 12).
reported in literature (Table S2, ESI†). It suggests that this
To further probe the size selectivity of MIL-101 (Cr), larger present protocol by combination of MIL-101 (Cr) as catalyst
size of aromatic aldehydes i.e. 1-naphthal- (Table 4, entry 15) and solvent free conditions is advantageous in MOF-catalysed
and 9-anthryl aldehydes (Table 4, entry 16) were used as cyanosilylations.
substrates. It is with no surprise that significant size selectivity
Heterogeneity and reusability of catalyst
is observed with MIL-101 (Cr) and yields for both substrates
decrease dramatically as compared with benzaldehyde in the In order to check if the cyanosilylation of carbonyl compounds
following order: benzaldehyde > 1-naphthaldehyde > 9- was promoted in a heterogeneous manner, we carried out a
anthraldehyde. The relative substrates dimension indicated filtration test. After a reaction time of 1 h, the reaction mixture
that the pore windows of MIL-101 (Cr) are large enough to was divided into two equal portions. One portion was stirred
allow benzaldehyde (8.21 × 5.83 Å)17 to diffuse swiftly through continuously. And the other portion was filtered and the
the channels to reach the catalytic active centres. In contrast, a filtrate was stirred under the same conditions. Both of which
significant decrease in reaction rate was observed for larger were monitored by GC analysis. The conversion of
size substrates. The yield for 1-naphthaldehyde (9.69 × 8.29 benzaldehyde was shown in Fig. 3. It revealed that the removal
Å)17 and 9-anthraldehyde (10.88 × 8.60 Å)17 reduced to 64% of MIL-101 (Cr) completely shut down the reaction. This result
and 19% under similar conditions, respectively. As evident for verified that the reaction was catalyzed in a heterogeneous
way.
Consequently, we shifted our attention to the reusability of
Table 4 Cyanosilylation of Aldehydes Catalyzed by MIL-101 (Cr).a
this heterogeneous catalyst and a recycling experiment was
carried out. After a reaction time of 4 h, the solid catalyst was
recovered by centrifugation, then washed with ethanol and
activated at 150 °C under vacuum for 12 h. The catalyst was
introduced into the reaction system again. The conversion of
benzaldehyde was analyzed by GC. After that, the procedure
was repeated for another two times. The conversion of
benzaldehyde in four consecutive runs was displayed in Fig. 4.
O
MIL-101 (Cr) (0.3 mol%)
neat, rt
NC
R
OTMS
H
+
TMSCN
R
H
Entry
R
Yieldb (%)
100
100
100
96
TONc
1
(CH3)2CH
n-C7H15
333
333
333
320
333
333
323
333
323
330
300
227
310
263
213
63
2
There is only
a slight decrease in the conversion of
3
cyclo-C6H10
C6H5
benzaldehyde in the latter three runs. Hence, MIL-101 (Cr) can
be recycled and reused for several times in the cyanosilylation
reaction.
4
5
2-NO2C6H4
2-ClC6H4
4-ClC6H4
3-FC6H4
100
100
97
Based on the experimental results and previously reported
6
7
8
100
97
9
4-FC6H4
100
80
10
11
12
13
14
15
16d
4-CF3C6H4
3-OCH3C6H4
4-OCH3C6H4
2-furanyl
2-thienyl
1-naphthyl
9-anthryl
99
90
68
60
93
79
40
Continuous reaction
64
Filtrate after 1 h
20
19
a Reaction conditions: aldehyde (1.0 mmol), TMSCN (1.2 mmol), catalyst (0.3
mol%), rt, 4 h.
0
0
2
4
6
8
10
Time (h)
b The yields were determined by 1H NMR spectroscopy.
c TON = yield/(mol% of metal ions).
Fig. 3 The filtration test of the cyanosilylation of benzaldehyde catalyzed by MIL-101
(Cr). Reaction conditions: benzaldehyde (1.0 mmol), TMSCN (1.2 mmol), MIL-101 (Cr)
(0.3 mol%), rt, and the conversion was monitored by GC analysis using tridecane as the
internal standard.
d The amount of TMSCN was 3.0 mmol.
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both Lewis acidities and pore sizes in MOFs are vital to the
catalytic activity. Taking both advantages, MIL-101 (Cr) was the
most active catalyst. In addition, the cyanosilylation of
aldehydes catalyzed by MIL-101 (Cr) was showed to be a
heterogeneous way, and MIL-101 (Cr) could be recycled and
reused for several times with a somewhat decrease in activity.
Using MIL-101 (Cr) as catalyst, a range of aldehydes was well
tolerated with this protocol, but for aromatic aldehydes with
large dimensions reacted much slowly due to size selectivity. It
is worthy of noting that the solvent free condition in MOFs
catalyzed cyanosilylation was superior to those in conventional
volatile solvents, which is more attractive to industrial
applications. Future studies will be directed toward developing
cheaper, more stable, or even chiral MOFs for asymmetric
transformations.
Time (hours)
Conversion (%)
100
80
60
40
20
0
4 h
4 h
4 h
4 h
1
2
3
4
Reaction cycle
Fig. 4 Recycling test of the cyanosilylation of benzaldehyde catalyzed by MIL-101 (Cr).
Reaction conditions: benzaldehyde (1.0 mmol), TMSCN (1.2 mmol), MIL-101 (Cr) (0.3
mol%), rt, 4 h.
Acknowledgements
results,17-18 a plausible reaction mechanism is proposed to
illustrate the process of MIL-101 catalyzed cyanosilylation
reaction. The labile water molecules in the channels of MIL-
101 (Cr) were removed by heating to expose the unsaturated
metal centres previously. The aldehydes were activated by the
coordinatively unsaturated Cr centres to react with TMSCN
(scheme 1). The products were replaced by aldehydes, and the
catalysts were continued to activate the aldehydes in the next
catalytic cycle.
This work was supported by the National Nature Science
foundation of China (No. 21376212, 21222601), Doctoral Fund
of Ministry of Education of China (No. 20120101120107) and
the Natural Science Foundation of Zhejiang Province, China
(No. LY13B060001).
Notes and references
1
(a) J. M. Brunel and I. P. Holmes, Angew. Chem., Int. Ed.,
2004, 43, 2752; (b) D. H. Ryu and E. J. Corey, J. Am. Chem.
Soc., 2004, 126, 8106; (c) M.
North,
Tetrahedron:
Asymmetry, 2003, 14, 147; (d) R. J. H. Gregory, Chem. Rev.,
1999, 99, 3649; (e) C. P. Decicco and P. Grover, Synlett, 1997,
529; (f) M. A. Schwindt, D. T. Belmont, M. Carlson, L. C.
Franklin, V. S. Hendrickson, G. L. Karrick, R. W. Poe, D. M.
Sobieray and J. V. D. Vusse, J. Org. Chem., 1996, 61, 9564; (g)
R. F. C. Brown, A. C. Donohue, W. R. Jackson and T. D.
McCarthy, Tetrahedron, 1994, 50, 13739; (h) Y. Lu, C. Miet,
N. Kunesch and J. E. Poisson, Tetrahedron: Asymmetry, 1993,
Conclusions
In conclusion, we have carried out a comprehensive study on
using different kinds of MOFs as catalysts for the
cyanosilylation of aldehydes with TMSCN. While these MOFs
tested are engineered with the same organic linker but with
different metal clusters, they showed different catalytic
activities. The FT-IR spectroscopic investigation showed that
4, 893; (i) W. R. Jackson, H. A. Jacobs, B. R. Matthews, G. S.
Jayatilake and K. G. Watson, Tetrahedron Lett., 1990, 31,
1447; (j) W. R. Jackson, H. A. Jacobs, G. S. Jayatilake, B. R.
Matthews and K. G. Watson, Aust. J. Chem., 1990, 43, 2045.
(a) W. T. Wang, X. H. Liu, L. L. Lin and X. M. Feng, Eur. J. Org.
Chem., 2010, 4751; (b) N. U. H. Khan, R. I. Kureshy, S. H. R.
Abdi, S. Agrawal and R. V. Jasra, Coord. Chem. Rev., 2008,
252, 593.
MIL-101 (Cr) Catalyst
2
H
O
R
O
3
4
M. North, D. L. Usanov and C. Young, Chem. Rev., 2008, 108,
5146.
(a) X. H. Geng, H. Zhou, P. R. Chen and Q. Xu, Chin. J. Org.
Chem., 2008, 28, 1157; (b) J. Gawronski, N. Wascinska and J.
Gajewy, Chem. Rev., 2008, 108, 5227; (c) F. X. Chen and X. M.
R
H
TMSCN
F/OH
Feng, Curr. Org. Synth., 2006, 3, 77; (d) F. X. Chen and X. M.
H
H
Feng, Synlett, 2005, 892; (e) F. Effenberger, Angew. Chem.,
Int. Ed., 1994, 33, 1555; (f) M. North, Synlett, 1993, 807.
(a) Z. G. Zhang, K. M. Lippert, H. Hausmann, M. Kotke and P.
R. Schreiner, J. Org. Chem., 2011, 76, 9764; (b) B. Bantu, D. R.
Wang, K. Wurst and M. R. Buchmeiser, Tetrahedron, 2005,
61, 12145; (c) D. E. Fuerst and E. N. Jacobsen, J. Am. Chem.
Soc., 2005, 127, 8964; (d) Y. H. Wen, X. Huang, J. L. Huang, Y.
Xiong, B. Qin and X. M. Feng, Synlett, 2005, 2445.
(a) H. Furukawa, K. E. Cordova, M. O'Keeffe and O. M. Yaghi,
Science, 2013, 341, 1230444; (b) G. Férey, Chem. Soc. Rev.,
2008, 37, 191; (c) M. J. Rosseinsky, Microporous Mesoporous
Mater., 2004, 73, 15; (d) J. L. C. Rowsell and O. M. Yaghi,
R
O
O
R
C
5
6
N
C
N
N
Si
Si
Si
C
Scheme
1
Proposed mechanism for the cyanosilylation reaction of carbonyl
compounds catalyzed by MIL-101 (Cr).
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DOI: 10.1039/C5RA13102B
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Microporous Mesoporous Mater., 2004, 73, 3; (e) S. L. James,
Chem. Soc. Rev., 2003, 32, 276.
RSC Advances
7
(a) J. W. Liu, L. F. Chen, H. Cui, J. Y. Zhang, L. Zhang and C. Y.
Su, Chem. Soc. Rev., 2014, 43, 6011; (b) H. C. Zhou, J. R. Long
and O. M. Yaghi, Chem. Rev., 2012, 112, 673; (c) L. Q. Ma and
W. B. Lin, Top. Curr. Chem., 2010, 293, 175; (d) Y. Liu, W. M.
Xuan and Y. Cui, Adv. Mater., 2010, 22, 4112; (e) S. Horike,
M. Dincǎ, K. Tamaki and J. R. Long, J. Am. Chem. Soc., 2008,
130, 5854.
8
9
M. Fujita, Y. J. Kwon, S. Washizu and K. Ogura, J. Am. Chem.
Soc., 1994, 116, 1151.
(a) G. Nickerl, A. Henschel, R. Grünker, K. Gedrich and S.
Kaskel, Chem. Ing. Tech., 2011, 83, 90; (b) C. Janiak and J. K.
Vieth, New J. Chem., 2010, 34, 2366; (c) L. Q. Ma, C. Abney
and W. B. Lin, Chem. Soc. Rev., 2009, 38, 1248.
10 A. Henschel, K. Gedrich, R. Kraehnert and S. Kaskel, Chem.
Commun., 2008, 4192.
11 P. García-García, M. Müller and A. Corma, Chem. Sci., 2014,
5, 2979.
12 K. Barthelet, J. Marrot, D. Riou and G. Férey, Angew. Chem.,
Int. Ed., 2002, 41, 281.
13 T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M.
Henry, T. Bataille and G. Férey, Chem.—Eur. J., 2004, 10
1373.
,
14 (a) K. Yang, Q. Sun, F. Xue and D. H. Lin, J. Hazard. Mater.,
2011, 195, 124; (b) G. Férey, C. Mellot-Draznieks, C. Serre, F.
Millange, J. Dutour, S. Surblé and I. Margiolaki, Science, 2005,
309, 2040.
15 J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S.
Bordiga and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130,
13850.
16 R. K. Das, A. Aijaz, M. K. Sharma, P. Lama and P. K.
Bharadwaj, Chem.—Eur. J., 2012, 18, 6866.
17 G. Kumar and R. Gupta, Inorg. Chem., 2013, 52, 10773.
18 (a) R. F. D’Vries, N. Snejko, M. Iglesias, E. Gutiérrez-Puebla
and M. A. Monge, Cryst. Growth Des., 2014, 14, 2516; (b) L.
M. Aguirre-Díaz, M. Iglesias, N. Snejko, E. Gutiérrez-Puebla
and M. Á. Monge, CrystEngComm, 2013, 15, 9562; (c) R.
F.
D’Vries, V. A. de la Peña-O’Shea, N. Snejko, M. Iglesias, E.
Gutiérrez-Puebla and M. Á. Monge, Cryst. Growth Des., 2012,
12, 5535; (d) R. F. D'Vries, M. Iglesias, N. Snejko, E. Gutiérrez-
Puebla and M. A. Monge, Inorg. Chem., 2012, 51, 11349; (e)
J. A. Seckar and J. S. Thayer, Inorg. Chem., 1976, 15, 501.
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Table of Contents
(Key Topic)
ꢀ
Solvent free
Size-selective
Reusable
ꢀ
ꢀ
ꢀ
High TON
MIL-101 (Cr)
UiO-66 (Zr)
OTMS
O
MOFs
+
TMSCN
R
H
R
CN
neat, rt
H
MIL-47 (V)
MIL-53 (Al)
This paper presents a systematic investigation of the cyanosilylation of aldehydes with TMSCN by
using several MOFs as the catalysts.