An in-based 3D metal-organic framework as heterogeneous Lewis acid catalyst for multi-component Strecker reactions

Article abstract of DOI:10.1016/j.ica.2018.04.037

A novel three-dimensional metal-organic framework (MOF) {[In₃(NIPH)₃ (HNIPH)(OH)₂]·4H₂O}_n (1) (H₂NIPH = 5-nitroisophthalic acid) with one-dimensional channels was synthesized and structurally characterized. Importantly, it demonstrates excellent catalytic activity for the Strecker reactions of two or three components under mild conditions. Moreover, the catalytic recycling of 1 as a representative example was explored. It can be easily separated and reused for no less than five runs with more than 80% conversion yield in catalytic ability.

Full text of DOI:10.1016/j.ica.2018.04.037

Accepted Manuscript
Research paper
An In-based 3D metal-organic framework as heterogeneous Lewis acid catalyst
for multi-component Strecker reactions
Juan Chai, Ping Zhang, Jianing Xu, Hui Qi, Jing Sun, Shubo Jing, Xiaodong
Chen, Yong Fan, Li Wang
PII:
S0020-1693(18)30055-0
https://doi.org/10.1016/j.ica.2018.04.037
ICA 18228
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
10 January 2018
17 April 2018
18 April 2018
Please cite this article as: J. Chai, P. Zhang, J. Xu, H. Qi, J. Sun, S. Jing, X. Chen, Y. Fan, L. Wang, An In-based
3D metal-organic framework as heterogeneous Lewis acid catalyst for multi-component Strecker reactions,
Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.04.037
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An In-based 3D metal-organic framework as heterogeneous
Lewis acid catalyst for multi-component Strecker reactions
Juan Chaia, Ping Zhanga, Jianing Xua, Hui Qib, Jing Suna, Shubo Jinga, Xiaodong
Chena, Yong Fana* and Li Wanga*
a College of Chemistry, Jilin University, Changchun 130012, Jilin, P. R. China.
E-mail: mrfy@jlu.edu.cn; lwang99@jlu.edu.cn.
b The Second Hospital of Jilin University, Changchun 130041, Jilin, P. R. China.
Abstract
A novel three-dimensional metal-organic framework (MOF) {[In3(NIPH)3
(HNIPH)(OH)2]·4H2O}n (1) (H2NIPH = 5-nitroisophthalic acid) with one-dimensional
channels was synthesized and structurally characterized. Importantly, it demonstrates
excellent catalytic activity for the Strecker reactions of two or three components under
mild conditions. Moreover, the catalytic recycling of 1 as a representative example
was explored. It can be easily separated and reused for no less than five runs with
more than 80% conversion yield in catalytic ability.
Keywords: metal-organic framework; structure; Strecker reactions; catalyst
1. Introduction
Metal-organic frameworks (MOFs) are crystalline hybrid materials consisting of
discrete inorganic metal-containing nodes and multidentate organic ligands
(linkers)[1-3]. As an emerging class of crystalline materials, MOFs have gained
tremendous attention and become one of the fastest growing fields in both chemistry
1

and materials over the last two decades owing to their periodic structure and high
thermal stability [4-11]. It has been known that various factors, such as temperature,
solvent, additive templating, metal-to-ligand ratio, coordination geometries of metal
centers, coordinated modes of organic ligands, etc., can impose a great influence on
the self-assembly process, which is responsible for the variation of properties of
MOFs significantly [12]. Over the last few years, it has been reported that MOFs can
catalyze various organic reactions such as Cyanosilylation, Acetalization,
Knoevenagel condensation reactions, Coupling reactions of CO2, Strecker reactions
and so on [13-15].
Some functional MOFs have been developed as efficient heterogeneous catalysts
capable of catalyzing various organic reactions for the following reasons: 1) the
ordered porous structures can facilitate the accessibility of substrates to active sites;
and 2) metal ions can serve as Lewis acid to activate substrates [16-20]. In this regard,
the choices of metals and ligands are crucial to constructing MOFs of catalytic
function. In3+ ions have rather flexible coordination spheres and usually adopt various
coordination numbers, which affords active Lewis acid catalysis center for various
organic reactions [21,22]. Moreover, 5-nitroisophthalic acid (H2NIPH), closed to
benzene-1, 3, 5 tricarboxylic acid (H3BTC), has multiple coordination sites that may
generate structures of higher dimensions [23]. Nitryl groups (-NO2) coexisting in
isophthalic acid probably act as a hydrogen bond acceptor and also take on some
spatial effects in the formation of MOFs [24]. In some previous reports, it has been
validated to be a proper polydentate bridging ligand for the formation of
multidimensional MOFs [25-29]. In-based MOFs with high-connectivity may afford
active Lewis acid catalysis centers to perform catalytic activities [30-32].
2

Strecker reactions are one of the most common ways for the syntheses of
aminonitriles, which have been extensively employed as significant organic
intermediates for α-amino acids, β-amino acids, other nitrogen-containing
heterocycles etc. [33-35]. Thus, exploring efficient catalysts for Strecker reactions has
become a topic of great significance. Over the past decades, a variety of efficient
homogeneous and heterogeneous catalysts have been studied for Strecker reactions
[36-39]. Compared to conventional homogeneous catalysts, heterogeneous catalysts
have many advantages, including separation and catalyst reutilization, low toxicity,
especially for MOFs [40,41]. Li et al. reported that copper(I)/copper(II)-salen MOF
could be used as an efficient heterogeneous multifunctional catalyst for the synthesis
of aminonitriles via asymmetric three-component Strecker reactions with 99%
conversion rate [42]. Monge et al prepared a mesoporous In-MOF that can be reused
for 10 repeated experiments without significant loss of activity [43].
In this article, a novel MOF {[In3(NIPH)3(HNIPH)(OH)2]·4H2O}n (1) was
obtained based on H2NIPH and structurally characterized. 1 shows a 3D porous
framework with 1D channels. And catalytic performance of the obtained MOF was
investigated toward Strecker reactions. For the catalytic process, metal In (III) site
served as Lewis acid to activate aldimine or aldehyde, and the obtained MOF catalysts
exhibited excellent catalytic performance for Strecker reactions under mild conditions.
More importantly, 80% conversion rate of catalyst 1 was maintained after five
consecutive runs.
2. Experimental
2.1. Materials and instrumentation
3

All reagents and solvents were purchased from commercial sources without
further purification. Powder X-ray diffraction (PXRD) data were obtained using
SHIMADAZU XRD-6100 diffractometer with Cu Kα radiation (λ = 1.5418 Å).
Thermogravimetric analysis (TGA) was conducted on a Perkin-Elmer TGA 7
thermogravimetric analyzer with a heating rate of 10 °C min-1 from room temperature
to 800 °C. Fourier-transform infrared (FT-IR) spectra was measured on a Nicolet
Impact 410 spectrometer in the 4000-400 cm-1 range using the KBr pellet method.
Elemental analyses (C, H and N) were performed using an Elementar Vario EL cube
1
CHNOS Elemental Analyzer. H NMR spectra were recorded with a Bruker Avance
400 console at a frequency of 400 MHz. UV-vis absorption spectra were tested on a
Perkin-Elmer Lambda 950 spectrophotometer.
2.2. Synthesis
{[In3(NIPH)3(HNIPH)(OH)2]∙4H2O}n (1): A mixture of H2NIPH (0.0211 g, 0.1
mmol), InCl3∙4H2O (0.1 M, 1 ml) was added to CH3CN (4 ml), NaOH (1 M, 100 μl)
in a 23 ml Teflon-lined autoclave and then heated under autogenous pressure at
110 °C for three days, then cooled to room temperature under ambient conditions. The
colorless block crystals were obtained by filtration and washed with distilled water,
and dried in air. Yield: 70% for 1 (based on InCl3∙4H2O). Elemental analysis (%) for 1:
Anal. Calc.: C, 29.84; H, 1.79; N, 4.38; Found: C, 29.91; H, 1.87; N, 4.27.
2.3. Single crystal X-ray crystallography
Crystallographic data for 1 were collected on a Rigaku R-AXIS RAPID IP
diffractometer with graphite-monochromated Mo Kα (0.71073 Å) radiation at room
4

temperature. Structure was solved by direct methods and refined by full-matrix
least-squares fitting on F2 by the SHELXTL-97 crystallographic software package
[44]. All non-hydrogen atoms were refined with anisotropic displacement parameters.
The hydrogen atoms attached to C atoms were placed in calculated positions and
refined isotropically using a riding model with an Uiso(H) equivalent to 1.2 times of
Ueq(C). Approximately 26.9 % of the unit cell volume comprises a large region of the
disordered solvent which could not be modeled as discrete atomic sites. To resolve
this issue, solvent molecules were removed by SQUEEZE subroutine in PLATON
[45]. The final molecular formula of 1 was derived from crystallographic data
combined with elemental and thermogravimetric analyses data. Crystal detailed data
collection and refinement of 1 are summarized in Table S1.
Crystallographic data (excluding structure factors) for the structures of this work
have been submitted to Cambridge Crystallographic Data Centre, CCDC, 12 Union
Road, Cambridge CB21EZ, UK. Copies of the data can be obtained free of charge on
quoting the depository numbers CCDC-1560355 for 1 (Fax: +44-1223-336-033;
E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
2.4. Catalytic experiment
Sample 1 was soaked in CH3OH for 24 h at room temperature and then heated at
100 °C for 12 h under vacuum before the reaction to remove guest molecules from
pores and surface. The basic framework of 1 was retained after activation. For the
catalytic experiments, activated catalyst (0.0134 mmol), aldimine (0.14 mmol) and
trimethylsilyl cyanide (TMSCN) (47 μl) in CDCl3 (2.4 ml) were sequentially added to
a glass vial of 20 ml. The reaction mixtures were stirred at room temperature. The
1
reactions were monitored by H NMR spectroscopy and conversion yield was
5

determined from the ratio of the integral of the product signal in relation to the sum of
integrals of all signals (aldehyde, aldimine and products).
3. Results and discussion
3.1. Structural description
Scheme 1. Coordination modes of H2NIPH ligand in 1.
Fig. 1. (a) Coordination environments of In3+ ions in 1. Hydrogen atoms are omitted
for clarity. Symmetry mode: A = -x, y, 1-z; B = -0.5+x, 0.5-y, z. (b) 2D layer in 1. (c)
View of the 3D network along [001] direction. (d) Topology structure of 1.
Single-crystal analysis reveals that 1 crystallizes in monoclinic space group C2/m.
As shown in Fig. 1a, there are two kinds of metal atoms (In1 and In2) in the
6

asymmetric unit of 1, in which the In2 atom resides at a crystallographic inversion
center with an occupancy of 0.5. In1 ion is located in a octahedral geometry and
coordinated by four carboxylate oxygen atoms (O5, O5A, O10, O10A) from four
different NIPH2- ligands and two oxygen atoms (O1, O1A) from two OH groups, in
which O1, O1A, O5, O5A at the equatorial positions, O10 and O10A are at the axial
positions with an O(10)-In(1)-O(10A) angle of 179.053(151)°. In2 atom also displays
a slightly distorted octahedral coordination geometry, in which O1, O3, O7B, O12
atoms define the equatorial plane and two atoms O9A, O11 occupy vertex position.
Apexes bond angle of O9A-In2-O11 is 170.266(148)°. In-O bond length varies from
2.111(4) Å to 2.234(4) Å. [symmetry codes: (A) -x, y, 1-z; (B) -0.5+x, 0.5-y, z].
In 1, InO4 units are linked to each other through OH groups, giving an infinite
bent -In-OH-In-OH-chain (Fig. S7). These chains are further alternately linked by
NIPH2- ligands with conformations Ι and III to yield a layer along a axis (Fig. 1b).
HNIPH- ligands adopting bridge modes II pillared these 2D layers, resulting in the
formation of a single 3D network with 1D channels along c axis (Fig. 1c). From a
topological perspective, the ligand could be regarded as a 2-connected node, and each
In1 connecting two O1 atoms of OH groups can be considered as a two-connected
node. Each In2 connecting two ligands and O1, O2 atoms can be seen as a
four-connected node. Thus, the single 3D network can be described as a 2, 2,
4-connected network with a point symbol of {82.103.12}2 {8}3 (Fig. 1d).
N2 adsorption-desorption was performed with activated 1 given its 1D channels
structural nature [Fig. S10]. Although 1 contains sufficient window dimension (6 Å)
for diffusion of N2, it shows a low uptake [46-48].
3.2. Characterizations
7

Phase purity of as-synthesized 1 was confirmed by PXRD measurements, which
is in agreement with the simulated one (Fig. S1). TGA was performed on 1 under air
atmosphere with a heating rate of 10 °C min-1 from 25 to 800 °C. 1 releases OH
groups and free H2O molecules (8.1 wt.%) over the temperature range of 25-100 °C
(calc. 8.4 wt.%). Between 360 and 590 °C, 1 displays a continuous mass loss (55.2
wt.%), which corresponds to the loss of ligands in the framework (calc. 58.9 wt.%)
(Fig. S6).
FT-IR spectrum of 1 shows the characteristic bands of nitro groups and
carboxylic groups. In particular, nitro groups show absorption owing to asymmetric
and symmetric N-O stretching modes. Asymmetric modes typically result in a strong
band at 1532 cm-1, symmetric modes absorption peaks at 1347 cm-1 [49,50]. The
absorption band appeared at 1630 cm−1 was attributed to the C=O stretching vibration.
The absorption bands at 1080 cm-1 corresponded to the C-O stretching vibration [51]
(Fig. S4), all of which are consistent with the results of single-crystal X-ray analysis.
Chemical stability of 1 was expected to play a critical role in its catalytic
performance for the Strecker reactions. Herein, we evaluated the stability of 1 by
immersing the samples in various organic solvents, including DMF, DMA, CH3OH,
C2H5OH, CH2Cl2, and CHCl3. PXRD patterns show that all experimental diffraction
peaks agree well with the simulated counterparts (Fig. S2), indicating that the
structure of 1 was retained after treatment with solvents.
3.3. Catalytic properties
Strecker reactions, as a class of important organic reactions for synthesis of
amino acids, have aroused ample attention [52,53]. Strecker reactions are well known
as Lewis acid or base catalyzed C-C bond formation. In the past decades, numerous
8

homogeneous catalysts, such as metal salts, metal-salen complexes, metal oxides,
have been extensively utilized for Strecker reactions of aldimines [54-58]. Moreover,
some MOFs with open metal sites have also shown high catalytic efficiencies for
Strecker reactions in the presence of organic solvents [59-61]. A comparison of the
catalytic performance of different MOF catalysts in Strecker reactions is shown in
Table S2. Given the rich coordination unsaturated In3+ in 1, the catalytic performance
of the Strecker reactions was investigated with low catalyst loading and mild
temperature conditions.
To evaluate the effectiveness of the fresh and activated 1 as catalysts, their
catalytic activities were compared in Table S4. From the Table S4, we can conclude
that the catalytic performance is significantly improved after activation.
Table 1. Strecker reaction of various aldimines catalyzed by activated 1a.
entry
1c
aldimine
reaction time (h)
24
conversion yield(%)b
trace
2
24
96
9

3
4
24
24
92
53
5
6
24
24
28
93
7
8
24
24
16
38
9
24
24
98
84
10
10

11
24
66
a Reaction conditions unless specified otherwise: aldimine (0.14 mmol), TMSCN (47 μl),
catalyst (0.0134 mmol), CDCl3 (2.4 ml) at room temperature. b Yields were calculated by 1H NMR
with aldimines. c Same reaction conditions without catalyst 1.
As shown in Table 1, initial reaction was performed at room temperature.
Benzylidene-phenyl-amine reacted with TMSCN and gave rise to 96% conversion
rate of Phenyl-phenylamino-acetonitrile after 24 h (Table 1, entry 2). Noticeably,
when the reactions were carried out without catalysts, it is hardly to yield any target
products (Fig. 2, Table 1, entry 1), indicating the high catalytic performance of
activated 1 with respect to Strecker reactions.
Considering the high catalytic activity of activated 1 toward the Strecker reaction
of aldimine with TMSCN, various aldimines with different substitution groups were
further selected as reaction substrates. The electron-donating group (-OCH3) gave
higher yields whereas the electron-withdrawing group (-CF3) decreased yields with
respect to aldimine. Aldimine derivatives bearing electron-donating groups (-OCH3)
were converted to catalytic products with a higher conversion rate (92%) after 24 h
(Table 1, entry 3).
When sterically more demanding substrate aldimines were used, conversion rates
were obviously reduced (Table 1, entries 8 and 11), which may be ascribed to the fact
that these aldimines cannot easily approach the active sites within 1 due to its larger
bulkiness than the others.
11

Fig. 2. Conversion of benzylidene-phenyl-amine in the Strecker reaction catalyzed by
1 (green) and by the filtrate of 1 after 5 h of the reaction (red). Reaction conditions:
aldimine (0.14 mmol), TMSCN (47 μl), CDCl3 (2.4 ml), Cat.1 (0.0134 mmol), room
temperature.
To clarify the heterogeneity of the catalytic reaction, activated 1 was separated
by filtration when product conversion rate reached 24% (5 h) and then the reaction
continued on. A slight increase in product yield after 30 h (Fig. 2). Moreover, H2NIPH
ligand was not observed from UV-vis spectra of the filtrate, indicating that the present
Strecker reaction was indeed heterogeneous (Fig. S8).
Table 2. Strecker reaction of three-component catalyzed by activated 1a.
12

amine
reaction time (h) conversion yield (%)b
entry
1
aldehyde
24
7.5
24
24
94
93
61
44
2
3
4
5
6
24
24
91
18
7
8
24
24
51
57
9
24
91
13

10
24
19
a
Reaction conditions: aldehyde (0.14 mmol), aniline (0.14 mmol), TMSCN (47 μl), catalyst
b
1
(0.0134 mmol), CDCl3 (2.4 ml) at room temperature. Yields were calculated by H NMR with
aldehydes.
The three-component Strecker reactions also aroused great concerns.
Three-component Strecker reactions possess obvious advantages over binary reactions,
for example, the separation and purification of intermediate products are omitted and
the former method improves atom economy with broaden applicability [62]. Herein,
the three-component Strecker reactions were successfully carried out based on a series
of various aldehydes, amines and TMSCN by using one-pot protocol in the presence
of activated 1 at room temperature and gave good yields as summarized in Table 2.
Significantly, for the three-component Strecker reaction of aromatic aldehydes with
an electron-donating group (i.e. -OCH3, -CH3), anilines and TMSCN, the catalytic
conversion rate can only reach 44% and 51%, respectively (Table 2, entries 4 and 7).
Moreover, amines such as 4-methoxyl-phenylamine were also utilized as substrates in
the reactions. Notably, 4-methoxyl-phenylamine and aldehyde showed a much higher
conversion
rate
(93%
and
91%)
in
comparison
to
that
of
4-trifluoromethyl-phenylamine (61% and 18%), indicating that electron group types
also have effects on the catalytic performance (Table 2, entries 2, 3 and 5, 6).
Stability and recyclability of activated 1 were further investigated by using
benzaldehyde and aniline as substrate. After a 24 h catalytic reaction, activated 1 was
isolated by filtration and washed with methanol and reused for the next reaction. More
than 80% yield was retained even after five consecutive runs (Fig. S9). Moreover,
14

PXRD patterns before and after the catalytic reactions indicate that structure of
activated 1 was maintained after recycle reactions (Fig. S3).
4. Conclusions
In summary, a stable 3D In-based 1 with 1D channels was produced with rich
open Lewis acid sites. It exhibited higher catalytic activities as an efficient
heterogeneous catalyst for the multi-component Strecker reactions under mild
conditions. Importantly, activated 1 shows much higher catalytic activities to aldimine
derivatives with electron-donating groups in comparison to those with
electron-withdrawing groups in two-component Strecker reaction catalytic process.
With increasing size of reaction substrates, conversion rates were suppressed
obviously. Moreover, in the three-component Strecker reaction, catalyst 1 can be
reused up to five times with comparable stability. The excellent catalytic activity and
good stability demonstrate that 1 is an efficient heterogeneous catalyst for
α-aminonitriles formation at room temperature.
Acknowledgments
The authors gratefully acknowledge the financial support through the National
Natural Science Foundation of China (Grant Nos. 21171065, 21201077 and
21401005).
References
[1] Q.H. Yang, Q. Xu. H.L. Jiang, Chem. Soc. Rev. 46 (2017) 4774.
[2] S.Ø. Ødegaard, G.C. Shearer, D.S. Wragg, K.P. Lillerud, Chem. Soc. Rev. 46
(2017) 4867.
15

[3] L.M.A. Díaz, D.R. Fisac, M. Iglesias, E.G. Puebla, F. Gándara, N. Snejko, M.Á.
Monge, Coord. Chem. Rev. 335 (2017) 1.
[4] A. Dhakshinamoorthy, M. Alvaro, H. Garcia, Chem. Commun. 48 (2012) 11275.
[5] D.M. Jiang, T. Mallat, F. Krumeich, A. Baiker, J. Catal. 257 (2008) 390.
[6] J. Kim, S. Bhattacharjee, K.E. Jeong, S.Y. Jeong, W.S. Ahn, Chem. Commun. 0
(2009) 3904.
[7] L.X. Shi, C.D. Wu, Chem. Commun. 47 (2011) 2928.
[8] J. Park, J.R. Li, Y.P. Chen, J.M. Yu, A.A. Yakovenko, Z.U. Wang, L.B. Sun, P.B.
Balbuena, H.C. Zhou, Chem. Commun. 48 (2012) 9995.
[9] Y.X. Tan, Y.P. He, J. Zhang, Chem. Mater. 24 (2012) 4711.
[10] P.Z. Li, X.J. Wang, J. Liu, J. Liang, J.Y.J. Chen, Y.L. Zhao, CrystEngComm 19
(2017) 4157.
[11] S.M.J. Rogge, A. Bavykina, J. Hajek, H. Garcia, A.I.O. Suarez, A.S. Escribano,
A. Vimont, G. Clet, P. Bazin, F. Kapteijn, M. Daturi, E.V.R. Fernandez, F.X.L.i Xamena,
V.V. Speybroeck, J. Gascon, Chem. Soc. Rev. 46 (2017) 3134.
[12] J.M. Roberts, O.K. Farha, A.A. Sarjeant, J.T. Hupp, K.A. Scheidt, Cryst. Growth
Des. 11 (2011) 4747.
[13] Y. Cao, Z.Q. Zhu, J.N. Xu, L. Wang, J.Y. Sun, X.B. Chen, Y. Fan, Dalton Trans.
44 (2015) 1942.
[14] J. Park, J.R. Li, Y.P. Chen, J.M. Yu, A. A. Yakovenko, Z.Y.U. Wang, L.B. Sun, P.
B. Balbuenab, H.C. Zhou, Chem. Commun. 48 (2012) 9995.
[15] X.X. Gao, M.S. Liu, J.W. Lan, L. Liang, X. Zhang, J.M. Sun. Cryst. Growth Des.
17 (2017) 51.
[16] C.D. Wu, M. Zhao, Adv. Mater. 0 (2017) 1605446.
[17] W. Jiang, J. Yang, Y.Y. Liu, S.Y. Song, J.F. Ma, Inorg. Chem. 56 (2017) 3036.
16

[18] Y. Liu, K. Mo, Y. Cui, Inorg. Chem. 52 (2013) 10286.
[19] W.Z. Qiao, H. Xu, P. Cheng, B. Zhao, Cryst. Growth Des. 17 (2017) 3128.
[20] J.A. Johnson, B.M. Petersen, A. Kormos, E. Echeverria, Y.S. Chen, J. Zhang, J.
Am. Chem. Soc. 138 (2016) 10293.
[21] F. Gándara, B.G. Lor, E.G. Puebla, M. Iglesias, M.Á. Monge, D.M. Proserpio, N.
Snejko, Chem. Mater. 20 (2008) 72.
[22] J. Xia, J.F. Zheng, J.N. Xu, L. Wang, L. Yang, Z.D. Su, Y. Fan, Inorg. Chim. Acta
411 (2014) 35.
[23] X.F. Zhu, N. Wang, B. Li, H. Zhang, Y.H. Luo, Y. Pang, D. Tian, Inorg. Chim.
Acta 383 (2012) 235.
[24] S.P. Chen, S.A. Qi, S.L. Gao, Z. Anorg. Allg. Chem. 634 (2008) 1591.
[25] X.Y. Lu, J.W. Ye, W. Li, W.T. Gong, L.J. Yang, Y. Lin, G.L. Gui,
CrystEngComm 14 (2012) 1337.
[26] D. Sarma, S. Natarajan, Cryst. Growth Des. 11 (2011) 5415.
[27] Y.X. Ren, S.P. Chen, G. Xie, S.L. Gao, Q.Z. Shi, Inorg. Chim. Acta 359 (2006)
2047.
[28] Q. Gao, M.Y. Wu, Y.G. Huang, L. Chen, W. Wei, Q.F. Zhang, F.L. Jiang, M.C.
Hong, CrystEngComm 11 (2009) 1831.
[29] H. Abourahma, B. Moulton, V. Kravtsov, M.J. Zaworotko, J. Am. Chem. Soc.
124 (2002) 9990.
[30] H.N.K. Lam, N.B. Nguyen, G.H. Dang, T. Truong, N.T.S. Phan, Catal. Lett. 146
(2016) 2087.
[31] L.M.A. Díaz, M. Iglesias, N. Snejko, E.G. Puebla, M.Á. Monge, CrystEngComm
15 (2013) 9562.
17

[32] L.M.A. Díaz, M. Iglesias, N. Snejko, E.G. Puebla, M.Á. Monge, RSC Adv. 5
(2015) 7058.
[33] A. Heydari, P. Fatemi, A.A. Alizadeh, Tetrahedron Lett. 39 (1998) 3049.
[34] Y.Μ. Shafran, V.A. Bakulev, V.S. Mokrushin, Russ. Chem. Rev. 58 (1989) 148.
[35] A. Mishra, A. Ali, S. Upreti, M.S. Whittingham, R. Gupta, Inorg. Chem. 48 (2009)
5234.
[36] L.M.A. Díaz, M. Iglesias, N. Snejko, E.G. Puebla, M.Á. Monge, Chem. Eur. J. 22
(2016) 6654.
[37] J. Blacker, L.A. Clutterbuck, M.R. Crampton, C. Grosjean, M. North,
Tetrahedron: Asymmetry 17 (2006) 1449.
[38] D.S. Deng, H. Guo, G.H. Kang, L.F. Ma, X. He, B.M. Ji, CrystEngComm 17
(2015) 1871.
[39] J. Choi, H.Y. Yang, H.J. Kim, S.U. Son, Angew. Chem. Int. Ed. Engl. 49 (2010)
7718.
[40] A. Bhunia, M.A. Gotthardt, M. Yadav, M.T. Gamer, A. Eichhofer, W. Kleist, P.W.
Roesky, Chem. Eur. J. 19 (2013) 1986.
[41] J. Xia, J.N. Xu, Y. Fan, T.Y. Song, L. Wang, J.F. Zheng, Inorg. Chem. 53 (2014)
10024.
[42] Y.L. Hou, R.W.Y. Sun, X.P. Zhou, J.H. Wang, D. Li, Chem. Commun. 50 (2014)
2295.
[43] D.R. Fisac, L.M.A. Díaz, M. Iglesias, N. Snejko, E.G. Puebla, M.Á. Monge, F.
ndara, J. Am. Chem. Soc. 138 (2016) 9089.
[44] G. Sheldrick, University of Goettingen, Goettingen, Germany, 1997.
[45] A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7.
18

[46] D.K. Maity, A. Halder, B. Bhattacharya, A. Das, D. Ghoshal, Cryst. Growth Des.
16 (2016) 1162.
[47] L. Mathivathanan, J.T. King, J.N.P. Pedrozo, O.J.G. Ricard, A.J.H. Maldonado, J.
A. Santana, R.G. Raptis, Cryst. Growth Des. 13 (2013) 2628.
[48] F. Su, C.Y. Zhou, C. Han, L.T. Wu, X. Wu, L. Sun, J. Su, S.S. Feng, L.P. Lu, M.L.
Zhu, CrystEngComm 20 (2018) 1818.
[49] J. Zhang, S. Yao, S. Liu, B. Liu, X.D. Sun, B. Zheng, G.H. Li, Y. Li, Q.S. Huo,
Y.L. Liu, Cryst. Growth Des. 17 (2017) 2131.
[50] P.D. Yi, H.L. Huang, Y.G. Peng, D.H. Liu, C.L. Zhong, RSC Adv. 6 (2016)
111934.
[51] O.V. Zalomaeva, A.M. Chibiryaev, K.O. Kovalenko, O.A. Kholdeeva, B.S.
Balzhinimaev, V.P. Fedin, J. Catal. 298 (2013) 179.
[52] H. Groger, Chem. Rev. 103 (2003) 2795.
[53] L. Yet, Angew. Chem. Int. Ed. Engl. 40 (2001) 875.
[54] M.S. Sigman, E.N. Jacobsen, J. Am. Chem. Soc. 120 (1998) 5315.
[55] N.S. Josephsohn, K.W. Kuntz, M.L. Snapper, A.H. Hoveyda, J. Am. Chem. Soc.
123 (2001) 11594.
[56] V. Banphavichit, W. Mansawat, W. Bhanthumnavin, T. Vilaivan, Tetrahedron 60
(2004) 10559.
[57] C.A. Krueger, K.W. Kuntz, C.D. Dzierba, W.G. Wirschun, J.D. Gleason, M.L.
Snapper, A.H. Hoveyda, J. Am. Chem. Soc.121 (1999) 4284.
[58] H. Ishitani, S. Komiyama, Y. Hasegawa, S. Kobayashi, J. Am. Chem. Soc. 122
(2000) 762.
[59] L.M.A. Díaz, F. ndara, M. Iglesias, N. Snejko, E.G. Puebla, M.Á. Monge, J.
Am. Chem. Soc. 137 (2015) 6132.
19

[60] A.P. Singh, A. Ali, R. Gupta, Dalton Trans. 39 (2010) 8135.
[61] S.Y. Wang, J.N. Xu, J.F. Zheng, X.D. Chen, L. Shan, L.J. Gao, L. Wang, M. Yu,
Y. Fan, Inorg. Chim. Acta 437 (2015) 81.
[62] M.J. Climent, A. Corma, S. Iborra, RSC Adv. 2 (2012) 16.
20

Graphical abstract and legend
An In-based 3D metal-organic framework as heterogeneous Lewis
acid catalyst for multi-component Strecker reactions
Juan Chaia, Ping Zhanga, Jianing Xua, Hui Qib, Jing Suna, Shubo Jinga, Xiaodong
Chena, Yong Fana* and Li Wanga*
a College of Chemistry, Jilin University, Changchun 130012, Jilin, P. R. China.
E-mail: mrfy@jlu.edu.cn; lwang99@jlu.edu.cn.
b The Second Hospital of Jilin University, Changchun 130041, Jilin, P. R. China.
A novel three-dimensional metal-organic framework based on 5-nitroisophthalic acid
ligand has been prepared under solvothermal condition. It can be as Lewis acid
21

catalyst and show good catalytic activity for the multi-component Strecker reactions.
Especially, it can obtain more than 80% conversion yields after five consecutive runs.
Highlights
1. In-base metal-organic framework (MOF) 1 has been successfully synthesized. 1
features a 3D framework with 1D channels.
2. 1 performs as Lewis acid catalyst on multi-component Strecker reactions.
3. 1 displays good catalytic activity for heterogeneous multi-component Strecker
reactions with more than 80% conversion yields after five runs.
22