Polyoxometalate immobilized on MOF-5 as an environment-friendly catalyst for the synthesis of poly-functionalized 3-pyrrolin-2-ones

Article abstract of DOI:10.1002/aoc.6064

A polyoxometalate immobilized on MOF-5 (POM/MOF-5) material has been synthesized and evaluated for the diversity-oriented synthesis of poly-functionalized 3-pyrrolin-2-ones via pseudo-four-component reaction between dialkyl acetylenedicarboxylate, amines, and aldehyde. The catalyst can be separated from the reaction mixture and reused at least five times with superior activity.

Full text of DOI:10.1002/aoc.6064

Received: 24 July 2020
DOI: 10.1002/aoc.6064
Revised: 11 September 2020
Accepted: 28 September 2020
F U L L P A P E R
Polyoxometalate immobilized on MOF-5 as an
environment-friendly catalyst for the synthesis of
poly-functionalized 3-pyrrolin-2-ones
Li Bao-Le1
| Hong-Yan Zhang2
| Jia-Qi Di2
| Zhan-Hui Zhang2
1Department of Radiochemistry, China
Institute of Atomic Energy, Beijing, China
2Hebei Key Laboratory of Organic
Functional Molecules, National
A polyoxometalate immobilized on MOF-5 (POM/MOF-5) material has
been synthesized and evaluated for the diversity-oriented synthesis of
poly-functionalized 3-pyrrolin-2-ones via pseudo-four-component reaction
between dialkyl acetylenedicarboxylate, amines, and aldehyde. The catalyst
can be separated from the reaction mixture and reused at least five times with
superior activity.
Demonstration Center for Experimental
Chemistry Education, College of
Chemistry and Material Science, Hebei
Normal University, Shijiazhuang, China
Correspondence
K E Y W O R D S
Zhan-Hui Zhang, College of Chemistry
and Material Science, Hebei Normal
University, Shijiazhuang 050024, China.
Email: zhanhui@hebtu.edu.cn
3-pyrrolin-2-ones, heterogeneous catalyst, MOF-5, multicomponent reaction, polyoxometalate
Funding information
Nature Science Foundation of Hebei
Province, Grant/Award Number:
B2020205026; National Natural Science
Foundation of China, Grant/Award
Number: 21272053
1 | INTRODUCTION
tunable pore distributions, abundant aromatic ligands,
outstanding thermal and solvent stabilities, high
Polyoxometalates (POM) are well-known catalysts
because of their unique redox properties, tunable acidity,
and possibility of the catalyst design at atomic/
molecular levels, which have been employed
rather extensively as catalysts for various organic
reactions over the past few decades, including
oxidation,[1] reduction,[2] multicomponent,[3] esterifica-
tion and transesterification,[4] and C–C coupling[5]
reactions. They could be designed as multifunctional
catalysts, based on different metal atoms or heteroatoms
in their structure, counter cations, second structures.[6]
However, the inherent shortcomings of their high
solubility, low surface area, and instability under reaction
conditions impeded the further application of POM-based
acid–base catalytic activities, and ease of func-
tionalization and design.[7] Recently, polyoxometalates/
metal–organic frameworks (POM/MOFs) materials have
been reported for several applications including proton
conduction,[8] gas storage/separation,[9] drug carriers,[10]
solid electrolytes,[11] photosensitizers,[12] and catalysis.[13]
Combining the high catalytic activity of particular POM
with the large surface area and stability of MOF to
develop a new efficient and environmentally friendly
catalyst for catalytic organic transformations is therefore
an interesting challenge.
Nitrogen-containing heterocycles are an important
structural unit and play an essential role in natural, phar-
maceutical, and coordination chemistry.[14] In particular,
pyrrole and pyrrolidine derivatives as five-membered
nitrogen-containing heterocycles are common core scaf-
folds in natural products and pharmaceutical agents.[15]
catalysts. Metal–organic frameworks (MOFs) as
a
promising catalyst support have drawn significant
attention because of their large specific surface areas,
Appl Organomet Chem. 2020;e6064.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
1 of 14
https://doi.org/10.1002/aoc.6064

2 of 14
BAO-LE ET AL.
2 | RESULTS AND DISCUSSION
2.1 | Preparation and characterization of
POM/MOF-5 catalyst
POM/MOF-5 composite catalyst was prepared by heating
H3PMo12O40, zinc nitrate, 1,4-benzenedicarboxylic acid
(H2BDC), and (CH3)4NOH at 180ꢀC for 24 h, which were
fully characterized by Fourier-transform infrared
spectroscopy (FTIR) spectra, powder X-ray diffraction
(XRD), scanning electron microscope (SEM), transmis-
sion electron microscopy (TEM) and SEM energy disper-
sive X-ray spectroscopy (EDS), and thermogram (TG).
The FTIR spectrum of pure H2BDC, H3PMo12O4,
MOF, and POM/MOF-5 is displayed in Figure 2. The
spectra of POM/MOF-5 contain not only typical infrared
bands belonging to MOF-5 but also Mo–O bands
appertaining to POM. The spectra of POM/MOF-5 dis-
played absorption peaks at 1062, 959, 879, and 802 cm−1
corresponding to the P O, Mo O, Mo–Ob–Mo, and
Mo–Oc–Mo band vibration of H3PMo12O40, respec-
tively.[38] The characteristic peaks related to MOF-5 and
H3PMo12O4 particles are slightly shifted. These shifts
indicate that a strong interaction exists between the POM
anion and MOF-5.
FIGURE 1 3-Pyrrolin-2-one
The 3-pyrrolin-2-one moiety (Figure 1) is
a
structural component found in a large number of natural
products including spongolactams,[16] oteromycin,[17]
echinophyllins,[18] and salipyrrolidinone A.[19] Moreover,
3-pyrrolin-2-ones that contain the γ-lactam ring have
proven to be useful scaffolds in the discovery of novel
drug entities, such as COX-II inhibitors,[20] VEGF-R
inhibitors,[21] HIV-1 integrase inhibitors,[22] HDAC
inhibitors,[23]
antitumor
agents,[24]
neurological
agents,[25] and novel G0/G1-phase arresting agents.[26]
Furthermore, the ring conjugate system of these
functionalized lactams favors its potential as intermedi-
ates in synthetic chemistry.[27] Therefore, synthetic
interest in 3-pyrrolin-2-ones arises from their occurrence
in nature, diverse biological activity, and utility as
building blocks for the preparation of nitrogen
heterocycles and γ-amino acid derivatives.[28]
Among the many synthetic approaches to
N-heterocycles, multicomponent coupling reaction that is
a powerful synthetic tool to provide structurally complex
molecules in a single pot has become increasingly
attractive.[29] Recently, a few protocols for synthesis poly-
functionalized 3-pyrrolin-2-ones via the four-component
reaction of dialkyl acetylenedicarboxylate, aldehyde,
and amines in the presence of lemon juice,[30]
The XRD patterns of POM, MOF-5, and POM/POM
are provided in Figure 3. Upon immobilizing of POM on
MOF-5, the main peaks contributed to POM and MOF-5
are observed, whereas the intensities of the peaks at low
angles decrease. These findings suggest the encapsulation
of POM in the cavities of MOF-5 and the intact of the
ordered structure of MOF-5.
As shown in Figure 4, the SEM of POM/MOF-5 cata-
lyst demonstrates that the particles are highly crystalline
UiO-66-SO3H,[31]
Cu
(OAc)2ÁH2O,[32]
perovskite-
structured BiFeO3 nanoparticles,[33] molecular iodine,[34]
TiO2 nanopowder,[35] or BF3/nano-sawdust[36] have been
developed. In continuation of our effort to develop
efficient and reusable heterogeneous catalysts for green
synthetic methods,[37] herein, we report on the
preparation of a POM/MOF-5 and its application as
a
heterogeneous catalyst for the synthesis of
poly-functionalized 3-pyrrolin-2-ones (Scheme 1).
SCHEME 1 POM/MOF-5-catalyzed four-component reaction
FIGURE 2 FTIR spectra of H2DBC, H3PMo12O40, MOF-5, and
of dialkyl acetylenedicarboxylate, aldehyde, and amines
POM/MOF-5

BAO-LE ET AL.
3 of 14
FIGURE 3 XRD pattern of H3PMo12O40,
MOF-5, and POM/MOF-5
FIGURE 4 SEM image of POM/MOF-5
FIGURE 5 TEM image of
POM/MOF-5
cubic structure, which was also in a good agreement with
the results from TEM (Figure 5). TEM and SEM images
collected demonstrate that POM encapsulation is limited.
EDS analysis indicates the presence of elements C, O,
Zn, P, and Mo (Figure 6). The presence of Mo confirms
the loading of PMo12 onto the MOF-5 surface or into the

4 of 14
BAO-LE ET AL.
FIGURE 6 EDX mapping image of POM/MOF-5
pores. Furthermore, element mapping was adopted in
order to further describe the spatial distribution and the
combination of MOF-5 and H3PMo12O4. The data
revealed the presence and homogeneous distribution of
POM clusters in these materials. The nitrogen
absorption–desorption measurements indicate that
POM/MOF-5 had a specific surface area of 165 m2g−1
(Figure 7).
POM/MOF-5 has good thermal stability, as can be
learned from the TG shown in Figure 8. TGA experi-
ments were carried out under an air atmosphere from
20ꢀC to 800ꢀC. The weight loss below 300ꢀC resulted
from the occluded (CH3)4N+ and water. POM/MOF-5
began to decompose above 450ꢀC, which is much
higher than the reaction temperatures of the synthesis
reaction.
2.2 | Optimization of reaction conditions
The activity of the prepared catalyst was tested for the
reaction of aniline (2.0 mmol), benzaldehyde (1.0 mmol),
and dimethyl but-2-ynedioate (1.0 mmol) at room tem-
perature. The reaction, as shown in Table 1, proceeded
very slowly in the absence of catalyst, and only a trace of
desired product 4a was found after heating for 6 h
(Table 1, entry 1). Different heterogeneous catalysts such
as Fe-MIL-101, UiO-66, Cu-BTC, IRMOF-3, MIL-53(Al),
and MOF-5 on the reaction were investigated and gave
the desired product 4a in 25%–43% yields (Table 1, entries
2–7). Pleasingly, when POM (Mo)/MOF-5 was used as
the catalyst, the reaction yield can be significantly
improved (91%; Table 1, entry 9). It was noted that when
the reaction was performed in the same conditions in
FIGURE 7 Nitrogen adsorption and desorption curves of
POM/MOF-5
FIGURE 8 Thermogram of POM/MOF-5

BAO-LE ET AL.
5 of 14
TABLE 1 Optimization of the
reaction conditionsa
Entry
1
Catalyst
Solvent
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
EtOH
Time (h)
6.0
Yield (%)b
no
trace
25
32
35
29
30
43
61
91
85
10
52
25
62
42
41
70
91
92
2
Fe-MIL-101
3.0
3
UiO-66
3.0
4
Cu-BTC
3.0
5
IRMOF-3
3.0
6
MIL-53(Al)
3.0
7
MOF-5
3.0
8
POM(W)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
POM (Mo)/MOF-5
3.0
9
3.0
10
11
12
13
14
15
16c
17d
18e
19f
3.0
DMF
3.0
CH3CN
THF
3.0
3.0
n-hexane
CH2Cl2
MeOH
MeOH
MeOH
MeOH
3.0
3.0
3.0
3.0
3.0
3.0
aReaction conditions: 1a (2.0 mmol), 2a (1.0 mmol), 3a (1.0 mmol), and 10-mg catalyst in the
solvent (2.0 mL) at room temperature for 3 h.
bIsolated yields.
c3-mg catalyst was used.
d5-mg catalyst was used.
e15-mg catalyst was used.
f50-mmol scale.
entry
8
with POM(W)/MOF-5, desired product
reaction scale to 50 mmol for the model reaction, and it
was found that the reaction yield reached the same level
as when it was performed on a small scale (Table 1, entry
19). Therefore, the optimal reaction conditions were
determined to be the following: 10 mg POM (Mo)/MOF-5
in 2 ml MeOH at room temperature for 3 h.
was obtained in low yield. Investigation of the
effect of solvents such as methanol, ethanol,
N,N-dimethylformamide (DMF), acetonitrile, tetrahydro-
furan, n-hexane, and dichloromethane showed that
methanol gave the best result for this transformation,
affording the product 4a in 91% yield (Table 1, entries
9–15). The yield was greatly affected by the amount of
catalyst. When 3.0 and 5.0 mg of the catalyst was used,
the yields were 41% and 70%, respectively (Table 1,
entries 16 and 17). And increasing the catalyst amount to
15 mg did not produce better results (Table 1, entry 18).
To demonstrate preparative utility, we also enlarged the
2.3 | Synthesis of poly-functionalized
3-pyrrolin-2-ones
Having the optimal conditions in hand, we investigated
the substrate scope of this reaction. As shown in Table 2,

6 of 14
BAO-LE ET AL.
TABLE 2 Substrate scope examinationa
Entry
R1
H
H
H
H
H
H
H
H
H
H
H
H
H
Aldehyde
R3
Product
4a
Time (h)
2.0
Yield (%)b
m.p. (ꢀC)
1
PhCHO
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
91
86
87
89
82
88
87
89
93
90
90
90
85
177–179 (178–180)[30]
180–182 (178–180)[33]
157–158
2
4-OCH3C6H4CHO
4-OEtC6H4CHO
4-C (CH3)3C6H4CHO
4-OHC6H4CHO
3-FC6H4CHO
4b
2.0
3
4c
2.5
4
4d
2.5
166–168
5
4e
2.0
194–196
6
4f
1.5
154–156
7
2-ClC6H4CHO
3-ClC6H4CHO
4-ClC6H4CHO
3-CF3C6H4CHO
4-NO2C6H4CHO
4-CNC6H4CHO
4g
3.0
144–146
8
4h
4i
2.5
179–181
183–184 (168–170)[35]
9
2.5
10
11
12
13
4j
2.5
166–167
4k
4l
2.5
156–158 (176–177)[32]
178–180
3.0
4m
3.5
160–162
14
15
H
H
Me
Me
4n
4o
3.5
4.0
86
84
158–160
200–202
16
17
H
H
Me
Me
4p
4q
5.0
5.0
83
81
190–192
172–174
18
H
Me
4r
4.5
84
138–139

BAO-LE ET AL.
7 of 14
TABLE 2 (Continued)
Entry
R1
Aldehyde
R3
Product
4s
Time (h)
Yield (%)b
m.p. (ꢀC)
19
H
Me
4.0
80
192–193 (183–184)[32]
20
21
22
23
24
25
26
27
28
29
30
31
32
33
4-CH3
4-OCH3
4-F
PhCHO
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Et
4t
4u
3.5
3.5
2.5
2.5
3.0
2.5
3.5
3.0
3.0
2.5
3.0
3.0
2.5
2.5
87
86
89
86
90
88
86
91
89
92
90
85
91
92
181–182 (182–184)[30]
159–161 (170–172)[30]
126–128 (133–134)[32]
139–140
PhCHO
PhCHO
4v
3-Cl
3-Br
4-Br
4-CH3
4-Br
4-CH3
4-Br
H
PhCHO
4w
4x
PhCHO
157–159
205–207 (203–205)[30]
PhCHO
4y
4-CH3C6H4CHO
4-CH3C6H4CHO
4-BrC6H4CHO
4-ClC6H4CHO
PhCHO
4z
183–185
4aa
4ab
4ac
4ad
4ae
4af
4ag
130–132
174–175 (146–148)[35]
222–223
130–131 (110–112)[30]
127–129 (107–108)[26]
175–176
H
3-OCH3C6H4CHO
3-BrC6H4CHO
PhCHO
Et
H
Et
4-Br
Et
151–153
aReaction conditions: 1 (2.0 mmol), 2 (1.0 mmol), 3 (1.0 mmol), and 10-mg POM (Mo)/MOF-5 in 2.0-mL MeOH at room temperature for
1.5-5.0 h.
bIsolated yields.
we first examined the reaction of anilines and dimethyl
but-2-ynedioate with a diverse array of aldehydes. All
of aldehydes with electron-donating or electron-
withdrawing substituents were found to be applicable to
this reaction and gave the expected products 4a–4s in
high to excellent yields. Remarkably, strongly electron-
poor aromatic aldehydes such as 4-(trifluoromethyl)benz-
aldehyde, 4-nitrobenzaldehyde, and 4-formylbenzonitrile
afforded the desired products 4j–4l in good yields.
The position of substituents has no obvious effect
(entries 7–9). Moreover, heterocycle substituted
aldehydes such as 2-thenaldehyde, 5-methylfuran-
the desired products 4p and 4q in 83% and 81%, respec-
tively. It is worth noting that disubstituted benzaldehyde
such as vanillin was also tolerated and gave the
corresponding product 4s in good yield. Next, a variety of
substituted anilines, such as para substituents (F, Br,
OMe, and CH3) and meta substituents (Cl and Br) were
examined. Electron-withdrawing and electron-donating
substituents were generally well tolerated, affording the
desired products 4t–4y in good yields. Stimulated by
these results, the reactions of substituted aromatic
aldehydes or substituted anilines were tested under the
above optimal conditions, giving the products 4z–4ac in
86%–92% yields. When the corresponding reactions of
DEAD were evaluated, similar results were obtained, as
expected (entries 30–33).
2-carbaldehyde,
4-pyridinecarboxaldehyde,
and
1,3-thiazole-2-carbaldehyde were also compatible in this
reaction, giving the desired products 4m–4o and 4r in
high yields. 2-Naphthaldehyde and 1,4-benzodioxan-
6-carboxaldehyde were also suitable partners and gave
Based
on
our
findings
and
previous
studies,[33] a possible reaction mechanism for this

8 of 14
BAO-LE ET AL.
SCHEME 2 Plausible reaction
mechanism for the synthesis of 4a
pseudo-four-component reaction is proposed. As shown
in Scheme 2, DMAD reacts with the first molecule of
aniline in the presence of POM (Mo)/MOF-5 through
the 1,4-addition reaction to lead to the formation of
hydroamination intermediate A. Simultaneously, an
imine B is produced through the condensation reaction
of the second molecule of aniline with the activated
benzaldehyde. During the reaction, POM (Mo)/MOF-5
acts as a Lewis acid, accepting a lone pair of electrons
from the nitrogen atom of the imine (B), resulting in
activation of the imine. POM (Mo)/MOF-5 is a more
efficient catalyst than POM(W)/MOF-5 in this reaction
because of more active Lewis acid properties. This acti-
vated imine B attacks on intermediate A through
Mannich-type reaction, leading to the formation of an
intermediate C. The intermediate C undergoes intramo-
lecular cyclization under the catalysis of POM (Mo)/
MOF-5 to obtain intermediate D, followed by tautomer-
ism to generate final product 4a.
reaction of anilines, benzaldehyde, and dimethyl but-
2-ynedioate, which exhibited the consistent activity for
the five consecutive cycles. In this procedure, the cata-
lyst was separated from the reaction mixture by simple
filtration. The recovered catalyst was washed with ethyl
acetate, dried under vacuum, and then reused directly
in model reaction for the next round without further
purification. The catalyst can be reused at least five
times with essentially no loss of catalytic activity, which
indicates that the prepared catalyst possessed excellent
activity and reusability.
After the sixth cycle, the reused catalyst was analyzed
by XRD, and the results showed that the catalyst fully
maintained its structural integrity (Figure 3). FTIR analy-
sis confirms the chemical integrity of the catalyst by com-
paring it with fresh catalyst (Figure 2). In order to
confirm the morphological stability of the catalyst, SEM
(Figure 4b) and TEM (Figure 5b) analyses were also per-
formed. The leaching amount of Mo and Zn was also
determined by inductively coupled plasma technology. It
was found that after the sixth cycle, the content of Mo
and Zn in methanol were 0.80 and 0.60 ppm, respectively.
These results indicate that the catalyst has excellent sta-
bility and durability and can be used multiple times in
catalytic conversion.
2.4 | Recyclability of the catalyst
As shown in Figure 9, reusability of the catalyst is
examined over POM (Mo)/MOF-5 with the model
FIGURE 9 Recycling of the catalyst

BAO-LE ET AL.
9 of 14
3 | CONCLUSION
The turbid mixture was sealed in a Teflonlined stainless
steel container and heated at 180ꢀC for 24 h, followed by
cooling to room temperature. After removal of the
mother liquor from the mixture, crystals were collected
and washed with water and EtOH and then dried under
vacuum at 125 ꢀC for 6 h.
In summary, we have developed a novel and efficient
protocol for one-pot synthesis of poly-functionalized
3-pyrrolin-2-ones using the recoverable POM/MOF-5 as
catalyst under mild condition. A variety of anilines and
various substituted aldehydes can be tolerated, giving the
structural diversity of poly-functionalized 3-pyrrolin-
2-ones in good to excellent yields. Moreover, the easy
recovery and reuse of the catalyst, short reaction time,
and ease of product separation make this solution
practical, environmentally friendly, and economically
attractive.
4.3 | General procedure for the synthesis
of poly-functionalized 3-pyrrolin-2-ones
The mixture of aldehyde (1.0 mmol), aniline (2.0 mmol),
and dimethyl but-2-ynedioate (1.0 mmol) and
POM/MOF-5 (10 mg) in MeOH (2 ml) at room tempera-
ture for 1–5 h is monitored by TLC. Upon completion of
the reaction, 5 ml of ethyl acetate was added. The product
was dissolved in ethyl acetate and the catalyst was sepa-
rated by simple filtration, washed with ethyl acetate, and
used for subsequent cycles after drying under vacuum.
Pure product was obtained by evaporation of the solvent,
followed by column chromatography on silica gel using
ethyl acetate/hexane as the eluent.
4 | EXPERIMENTAL
4.1 | Instruments and reagents
All chemicals and solvents were commercially available
from Merck, Aldrich, or Fluka as received and used
without further purification. X-ray diffraction analysis
was carried out using a D8 Advance diffractometer
(Bruker AXS, Germany). The surface morphology and
particle size were studied using a Hitachi S-4800 SEM
instrument (Hitachi Limited, Japan). Elemental compo-
sitions were determined using a Hitachi S-4800 SEM
equipped with an INCA 350 energy dispersive spec-
trometer (SEM-EDS) presenting a 133-eV resolution at
5.9 keV. TEM observation was performed using a
Hitachi H-7650 microscope at 80 kV (Hitachi Limited,
Japan). Melting points were measured on an X-5 digital
melting point apparatus (Gongyi, China) without cor-
rection. IR spectra were recorded in the range
4000–600 cm−1 using KBr pellets on a Bruker-TENSOR
27 spectrometer instrument (Bruker, Germany). 1H
NMR and 13C NMR spectra were recorded on Zhongke
Niujin AS 400 spectrometer (Wuhan, China) at 400 and
100 MHz, respectively, using CDCl3 as the solvent and
TMS as an internal standard. Mass spectra were
4.4 | Characterization data for unknown
products
4.4.1 | Methyl 2-(4-ethoxyphenyl)-5-oxo-
1-phenyl-4-(phenylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate (4c)
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.11 (s,
1H), 7.45 (d, J = 8.0 Hz, 2H), 7.32 (t, J = 8.0 Hz, 2H),
7.26–7.22 (m, 2H), 7.18–7.13 (m, 5H), 7.08 (t,
J = 7.5 Hz, 1H), 6.75 (d, J = 8.5 Hz, 2H), 5.77 (s, 1H),
3.94 (q, J = 7.0 Hz, 2H), 3.53 (s, 3H), 1.35 (t,
J = 7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 164.7,
164.0, 158.7, 141.8, 138.7, 136.5, 128.8, 128.7, 128.5,
128.3, 125.7, 124.7, 122.9, 122.8, 114.3, 109.5, 63.3, 62.7,
51.2, 14.9; IR (KBr): 3201, 3021, 1743, 1625, 1462, 1387,
performed on
a
ThermoFinnigan LCQ Advantage
1260,
1021,
875,
654,
538
cm−1
;
ESI-MS:
instrument (ThermoFinnigan, USA) with an ESI source
(4.5 KeV).
m/z = 429.5 (M + 1)+.
4.4.2 | Methyl 2-(4-(tert-butyl)phenyl)-
5-oxo-1-phenyl-4-(phenylamino)-
4.2 | Preparation of the POM/MOF-5
2,5-dihydro-1H-pyrrole-3-carboxylate (4d)
The POM/MOF-5 was prepared by the modified proce-
dure.[39] Typically, a mixture of Zn (NO3)2Á6H2O (0.416 g)
and H3PMo12O40ÁnH2O (0.2 g) in distilled water (10 mL)
was stirred for 15 min, and then H2BTC (0.174 g) and
(CH3)4NOH (0.09 g, 1.0 mmol) were added in succession
with stirring for another 30 min at room temperature.
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.10 (s, 1H),
7.50 (d, J = 8.0 Hz, 2H), 7.32 (t, J = 8.0 Hz, 2H), 7.27 (s,
1H), 7.25–7.23 (m, 3H), 7.18–7.13 (m, 5H), 7.08 (t,
J = 7.5 Hz, 1H), 5.80 (s, 1H), 3.54 (s, 3H), 1.24 (s, 9H);
13C NMR (100 MHz, CDCl3) δ 164.7, 164.2, 150.9, 141.8,

10 of 14
BAO-LE ET AL.
138.7, 136.7, 133.4, 128.8, 128.5, 127.1, 125.5, 125.4, 124.7,
122.9, 122.5, 109.7, 62.7, 51.2, 34.5, 31.3; IR (KBr): 3387,
4.4.6 | Methyl 2-(3-chlorophenyl)-5-oxo-
1-phenyl-4-(phenylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate (4h)
3269, 2924, 1721, 1604, 1542, 1443, 1341, 748, 538 cm−1
ESI-MS: m/z = 441.5 (M + 1)+.
;
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.20
(s, 1H), 7.44 (d, J = 8.5 Hz, 2H), 7.33 (t, J = 7.5 Hz,
2H), 7.29–7.15 (m, 9H), 7.10 (t, J = 7.5 Hz, 1H), 5.78
(s, 1H), 3.55 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 164.6, 163.9, 142.4, 139.1, 138.3, 136.2, 134.3, 129.8,
129.0, 128.5, 127.7, 126.0, 125.8, 125.1, 123.2, 122.7,
108.4, 62.5, 51.3; IR (KBr): 3465, 2924, 1735, 1621, 1456,
4.4.3 | Methyl 2-(4-hydroxyphenyl)-5-oxo-
1-phenyl-4-(phenylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate (4e)
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.09
(s, 1H), 7.43 (d, J = 8.0 Hz, 3H), 7.31 (t, J = 8.0 Hz,
4H), 7.25–7.13 (m, 4H), 7.10 (d, J = 9.0 Hz, 2H), 6.67
(d, J = 9.0 Hz, 2H), 5.76 (s, 1H), 3.53 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 164.8, 155.3, 141.9, 136.4, 128.9,
128.8, 128.6, 128.5, 125.8, 124.8, 123.0, 122.9, 120.9,
115.4, 62.7, 51.2; IR (KBr): 3350, 3053, 1705, 1655, 1406,
1328,
1235,
964,
877,
543
cm−1
;
ESI-MS:
m/z = 419.8 (M + 1)+.
4.4.7 | Methyl 5-oxo-1-phenyl-
4-(phenylamino)-2-(3-(trifluoromethyl)
phenyl)-2,5-dihydro-1H-pyr role-
3-carboxylate (4j)
1328,
1243,
904,
642,
511
cm−1
;
ESI-MS:
m/z = 401.4 (M + 1)+.
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.24 (s, 1H),
4.4.4 | Methyl 2-(3-fluorophenyl)-5-oxo-
1-phenyl-4-(phenylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate (4f)
7.53 (s, 1H), 7.43 (dt, J = 13.5, 6.5 Hz, 4H), 7.37
(d, J = 7.5 Hz, 1H), 7.33 (d, J = 7.5 Hz, 2H), 7.28 (s, 1H),
7.24 (s, 1H), 7.20 (d, J = 8.5 Hz, 3H), 7.10 (t, J = 7.5 Hz,
1H), 5.87 (s, 1H), 3.55 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 164.6, 163.8, 142.7, 138.2, 136.1, 130.6, 129.1,
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.19 (s, 1H),
3
7.44 (d, J = 8.0 Hz, 2H), 7.33 (t, J = 8.5 Hz, 2H),
7.28–7.15 (m, 6H), 7.10 (t, J = 7.5 Hz, 1H), 7.05
(d, J = 8.0 Hz, 1H), 6.96 (d, J = 9.5 Hz, 1H), 6.92–6.85
(m, 1H), 5.80 (s, 1H), 3.55 (s, 3H); 13C NMR (100 MHz,
128.6, 126.1, 125.3, 125.1 (q, JFC = 3.6 Hz), 124.8
3
(q, JFC = 3.7 Hz), 123.4, 122.8, 108.2, 62.6, 51.3; IR
(KBr): 3455, 3307, 2949, 1692, 1637, 1369, 1260, 1120,
932, 769, 532 cm−1; ESI-MS: m/z = 453.4 (M + 1)+.
1
CDCl3) δ 164.6, 163.94, 162.5 (d, JCF = 244.9 Hz), 142.3,
3
139.6 (d, JCF
=
6.7 Hz), 138.4, 136.3, 130.0
3
(d, JCF = 8.1 Hz), 129.0, 128.5, 126.0, 125.0, 123.4, 123.1,
122.7, 115.2 (d, 2JCF = 21.1 Hz), 114.5 (d, 2JCF = 22.1 Hz),
108.5, 62.6, 51.3; IR (KBr): 3387, 3260, 1690, 1602, 1370,
4.4.8 | 2-(4-cyanophenyl)-5-oxo-1-phenyl-
4-(phenylamino)-2,5-dihydro-1H-pyrrole-
3-carboxylate (4l)
1225,
1031,
853,
682,
513
cm−1
;
ESI-MS:
m/z = 403.4 (M + 1)+.
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.20 (s, 1H),
1
7.55 (d, J = 8.5 Hz, 2H), 7.43–7.39 (m, 3H), 7.34
(dd, J = 14.5, 6.5 Hz, 3H), 7.28 (s, 1H), 7.24 (s, 1H), 7.19
(t, J = 8.5 Hz, 3H), 7.11 (t, J = 7.5 Hz, 1H), 5.86 (s, 1H),
3.53 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 164.4, 163.8,
142.6, 138.1, 136.0, 132.4, 129.12, 128.5, 128.4, 126.2,
125.3, 123.3, 122.6, 118.5, 112.1, 107.6, 62.5, 51.3; IR
(KBr): 3387, 2230, 1701, 1645, 1500, 1372, 1228, 930, 853,
510 cm−1; ESI-MS: m/z = 410.4 (M + 1)+.
4.4.5 | Methyl 2-(2-chlorophenyl)-5-oxo-
1-phenyl-4-(phenylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate (4g)
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.27
(s, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.32 (dd, J = 18.0,
10.5 Hz, 4H), 7.20 (dd, J = 18.0, 10.0 Hz, 4H), 7.15–7.11
(m, 2H), 7.08 (t, J = 7.5 Hz, 1H), 7.05–6.98 (m, 1H),
6.50 (s, 1H), 3.55 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 164.7, 163.9, 142.9, 138.4, 136.3, 135.1, 134.4, 129.7,
129.3, 128.9, 128.5, 127.4, 127.0, 125.8, 125.0, 123.1,
122.3, 108.9, 58.0, 51.3; IR (KBr): 3487, 3269, 1704,
1621, 1433, 1302, 1221, 856, 738, 490 cm−1; ESI-MS:
m/z = 419.8 (M + 1)+.
4.4.9 | Methyl 5-oxo-1-phenyl-
4-(phenylamino)-2-(thiophen-2-yl)-
2,5-dihydro-1H-pyrrole-3-carboxylate (4m)
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.18 (s, 1H),
7.43 (d, J = 8.0 Hz, 2H), 7.31 (q, J = 8.0 Hz, 4H),

BAO-LE ET AL.
11 of 14
7.20–7.13 (m, 5H), 7.02 (d, J = 3.0 Hz, 1H), 6.83–6.81
(m, 1H), 6.13 (s, 1H), 3.58 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 164.6, 163.3, 142.2, 140.8, 138.4,
136.0, 128.9, 128.5, 127.5, 126.5, 126.2, 125.4, 125.0,
123.5, 123.1, 108.3, 58.7, 51.3; IR (KBr): 3388, 3057,
4.4.13 | Methyl 2-(2,3-dihydrobenzo[b][1,4]
dioxin-6-yl)-5-oxo-1-phenyl-
4-(phenylamino)-2,5-dihydro-1H-pyrrole-
3-carboxylate (4q)
1
1655, 1466, 1224, 860, 753, 495 cm−1
m/z = 391.5 (M + 1)+.
;
ESI-MS:
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.12 (s, 1H),
7.47 (d, J = 8.0 Hz, 2H), 7.30 (dd, J = 13.5, 5.5 Hz, 3H),
7.25 (d, J = 5.0 Hz, 1H), 7.15 (dd, J = 13.0, 7.5 Hz, 3H),
7.09 (t, J = 7.5 Hz, 1H), 6.78–6.67 (m, 3H), 5.71 (s, 1H),
4.18 (s, 4H), 3.55 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 164.7, 163.9, 143.4, 143.3, 141.9, 138.6, 136.5, 129.7,
128.9, 128.5, 125.7, 124.8, 122.9, 122.8, 120.8, 117.2, 116.2,
109.3, 64.1, 62.5, 51.2; IR (KBr): 3284, 3065, 2950, 1691,
4.4.10 | Methyl 2-(5-methylfuran-2-yl)-
5-oxo-1-phenyl-4-(phenylamino)-
2,5-dihydro-1H-pyrrole-3-carboxylate (4n)
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.21 (s, 1H),
1655, 1436, 1206, 954, 738, 487 cm−1
m/z = 443.5 (M + 1)+.
; ESI-MS:
7.42 (d, J = 7.5 Hz, 2H), 7.34–7.29 (m, 4H), 7.17
(dd, J = 13.5, 5.5 Hz, 4H), 6.17 (d, J = 7.0 Hz, 1H), 5.83
(s, 1H), 5.79 (d, J = 2.5 Hz, 1H), 3.61 (s, 3H), 2.16 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 164.8, 163.6, 152.2, 146.6,
142.8, 138.5, 136.4, 128.8, 128.4, 126.1, 124.9, 123.4, 123.1,
110.6, 106.4, 105.4, 57.2, 51.3, 13.6; IR (KBr): 3409, 2919,
4.4.14 | Methyl 5-oxo-1-phenyl-
4-(phenylamino)-2-(thiazol-2-yl)-
2,5-dihydro-1H-pyrrole-3-carboxylate (4r)
1624, 1453, 1232, 1352, 1190, 1088, 742, 498 cm−1
ESI-MS: m/z = 389.4 (M + 1)+.
;
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.37
(s, 1H), 7.63 (d, J = 3.0 Hz, 1H), 7.52 (d, J = 7.5 Hz,
2H), 7.36–7.28 (m, 4H), 7.24–7.17 (m, 4H), 7.14
(t, J = 7.5 Hz, 1H), 6.32 (s, 1H), 3.60 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 167.5, 164.6, 163.2, 143.3, 142.4,
138.0, 135.9, 129.0, 128.5, 126.3, 125.4, 123.5, 123.0,
120.7, 120.3, 105.9, 60.2, 51.5; IR (KBr): 3482, 3065,
1788, 1643, 1426, 1370, 739, 644, 530 cm−1; ESI-MS:
m/z = 392.4 (M + 1)+.
4.4.11 | Methyl 5-oxo-1-phenyl-
4-(phenylamino)-2-(pyridin-4-yl)-
2,5-dihydro-1H-pyrrole-3-carboxylate (4o)
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.50
(d, J = 4.5 Hz, 2H), 8.25 (s, 1H), 7.44 (d, J = 8.0 Hz,
2H), 7.33 (t, J = 7.5 Hz, 2H), 7.28 (s, 1H), 7.24 (s, 1H),
7.20–7.18 (m, 5H), 7.10 (t, J = 7.0 Hz, 1H), 5.80 (s, 1H),
3.54 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 164.3,
163.8, 150.0, 146.6, 142.6, 138.1, 136.0, 129.1, 128.5,
126.2, 125.3, 123.3, 122.6, 122.5, 107.3, 61.9, 51.3;
4.4.15 | Methyl 1-(3-bromophenyl)-
4-((3-bromophenyl)amino)-5-oxo-2-phenyl-
2,5-dihydro-1H-pyrrole-3-carboxylate (4x)
IR (KBr): 3376, 2920, 1607, 1450, 754, 680, 533 cm−1
ESI-MS: m/z = 386.4 (M + 1)+.
;
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.16 (s, 1H),
7.77 (s, 1H), 7.34–7.08 (m, 12H), 5.77 (s, 1H), 3.58 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 164.5, 163.7, 139.7, 137.7,
135.9, 130.1, 129.7, 128.7, 128.5, 127.9, 127.5, 125.9, 125.5,
122.5, 122.0, 121.7, 120.7, 62.9, 51.5; IR (KBr): 3327, 1695,
1621, 1477, 1411, 1024, 810, 676, 539 cm−1; ESI-MS:
m/z = 543.1 (M + 1)+.
4.4.12 | Methyl 2-(naphthalen-2-yl)-5-oxo-
1-phenyl-4-(phenylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate (4p)
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.20 (s, 1H),
7.80–7.71 (m, 4H), 7.49 (t, J = 8.5 Hz, 2H), 7.45–7.41
(m, 2H), 7.33 (t, J = 8.0 Hz, 2H), 7.27 (dd, J = 8.5, 1.5 Hz,
1H), 7.22–7.15 (m, 5H), 7.03 (t, J = 7.5 Hz, 1H), 5.98
(s, 1H), 3.49 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 164.7,
164.1, 142.2, 138.6, 136.5, 134.2, 133.2, 133.2, 128.9, 128.5,
127.9, 127.7, 126.2, 125.8, 124.9, 124.1, 122.9, 109.2,
63.3, 51.25 (s); IR (KBr): 3416, 3250, 2927, 1645, 1611,
4.4.16 | Methyl 5-oxo-1,2-di-p-tolyl-
4-(p-tolylamino)-2,5-dihydro-1H-pyrrole-
3-carboxylate (4z)
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.08
(s, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.13–7.02 (m, 10H),
5.73 (s, 1H), 3.54 (s, 3H), 2.33 (s, 3H), 2.25 (s, 3H),
2.22 (s, 3H); 13C NMR (100 MHz, CDCl3) 164.8, 163.9,
1460, 1328, 1205, 750, 552 cm−1
m/z = 435.5 (M + 1)+.
;
ESI-MS:

12 of 14
BAO-LE ET AL.
142.50, 137.7, 136.0, 135.3, 134.5, 134.0, 133.9, 129.4,
129.2, 129.0, 127.4, 123.1, 122.7, 108.5, 62.9, 51.1, 21.2,
21.0, 20.9; IR (KBr): 3310, 2946, 1694, 1633, 1377,
4.4.20 | Ethyl 2-(3-bromophenyl)-5-oxo-
1-phenyl-4-(phenylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate (4af)
1249,
814,
777,
524
cm−1
;
ESI-MS:
m/z = 427.4 (M + 1)+.
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.28 (s, 1H),
1
7.44 (s, 3H), 7.15–6.79 (m, 11H), 5.76 (s, 1H), 4.02
(s, 2H), 1.03 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
163.9, 163.5, 142.0, 139.0, 138.0, 135.9, 130.9, 130.6,
129.7, 128.7, 128.1, 125.7, 125.6, 124.6, 122.7, 122.3,
121.9, 121.5, 108.5, 62.0, 60.0, 13.5; IR (KBr): 3389, 3079,
4.4.17 | Methyl 1-(4-bromophenyl)-
4-((4-bromophenyl)amino)-5-oxo-
2-(p-tolyl)-2,5-dihydro-1H-pyrrole-
3-carboxylate (4aa)
1705, 1621, 1466, 1328, 1241, 859, 688, 499 cm−1
ESI-MS: m/z = 478.4 (M + 1)+.
;
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.14 (s, 1H),
7.43 (d, J = 8.5 Hz, 2H), 7.36 (s, 4H), 7.10 (d, J = 7.5 Hz,
2H), 7.05 (d, J = 8.5 Hz, 4H), 5.73 (s, 1H), 3.59 (s, 3H),
2.27 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 164.6, 163.7,
141.8, 138.2, 137.5, 135.6, 132.9, 131.9, 131.5, 129.4,
127.3, 124.5, 123.9, 119.0, 118.0, 110.3, 62.9, 51.4; IR
(KBr): 3411, 1706, 1677, 1633, 1492, 1366, 1298, 1241,
4.4.21 | Ethyl 1-(4-bromophenyl)-
4-((4-bromophenyl)amino)-5-oxo-2-phenyl-
2,5-dihydro-1H-pyrrole-3-carboxylate (4ag)
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.27
(s, 1H), 7.41–7.10 (m, 13H), 5.80 (s, 1H), 4.08 (s, 2H),
1.10 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 141.5,
135.3, 132.3, 132.1, 132.24–130.86 (m), 128.8, 128.4,
127.8, 127.4, 124.6, 124.2, 124.0, 123.6, 124.2, 63.1, 60.6,
13.6; IR (KBr): 3364, 3053, 1715, 1648, 1432, 1301,
1075,
922,
844,
493
cm−1
;
ESI-MS:
m/z = 427.4 (M + 1)+.
4.4.18 | Methyl 2-(4-bromophenyl)-5-oxo-
1-(p-tolyl)-4-(p-tolylamino)-2,5-dihydro-1H-
pyrrole-3-carboxylate (4ab)
1257,
1088,
879,
653,
429
cm−1
;
ESI-MS:
m/z = 557.2 (M + 1)+.
Yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.13
(s, 1H), 7.36 (d, J = 7.5 Hz, 2H), 7.28 (t, J = 8.0 Hz,
2H), 7.12–7.03 (m, 8H), 5.72 (s, 1H), 3.54 (s, 3H), 2.33
(s, 3H), 2.24 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
164.7, 163.7, 142.8, 136.3, 135.7, 134.9, 133.6, 131.6,
129.5, 129.3, 129.1, 123.3, 122.7, 121.9, 107.5, 62.4, 51.2,
21.0, 20.9; IR (KBr): 3290, 3019, 2252, 1693, 1651, 1399,
ACKNOWLEDGEMENTS
This work was financially supported by the National
Natural Science Foundation of China (No. 21272053) and
Nature Science Foundation of Hebei Province
(No. B2020205026).
AUTHOR CONTRIBUTIONS
1259,
843,
772,
519
cm−1
;
ESI-MS:
Li Baole: Data curation; investigation. Hong-Yan
Zhang: Methodology. Jia-Qi Di: Methodology.
Zhan-Hui Zhang: Project administration.
m/z = 492.4 (M + 1)+.
4.4.19 | Methyl 1-(4-bromophenyl)-
4-((4-bromophenyl)amino)-
CONFLICT OF INTEREST
There are no conflicts to declare.
2-(4-chlorophenyl)-5-oxo-2,5-dihydro-1H-
pyrrole-3-carboxylate (4ac)
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are
available from the corresponding author upon reasonable
request.
Yellow solid; 1H NMR (400 MHz, CDCl3)
δ 8.25 s, 1H), 7.50 (d, J = 8.5 Hz, 2H), 7.42
(q, J = 9.0 Hz, 4H), 7.30 (d, J = 8.5 Hz, 2H), 7.22
(d, J = 8.5 Hz, 2H), 7.12 (d, J = 8.5 Hz, 2H), 5.80
(s, 1H), 3.66 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
164.5, 163.5, 142.1, 137.2, 135.2, 134.8, 134.2, 132.1,
131.5, 129.0, 128.8, 124.8, 123.9, 119.2, 118.2, 109.4,
62.1, 51.5; IR (KBr): 3416, 1706, 1631, 1491, 1368,
ORCID
Li Bao-Le https://orcid.org/0000-0003-3704-8967
Hong-Yan Zhang https://orcid.org/0000-0003-2906-
4190
Jia-Qi Di https://orcid.org/0000-0001-7034-1212
Zhan-Hui Zhang https://orcid.org/0000-0002-1082-
5773
1295, 1242, 1071, 925, 847, 777 cm−1
m/z = 577.2 (M + 1)+.
; ESI-MS:

BAO-LE ET AL.
13 of 14
Catal. 2019, 9, 10174. d) C. T. Buru, O. K. Farha, ACS Appl.
Mater. Interfaces 2020, 12, 5345.
REFERENCES
[1] a) S. Goberna-Ferron, L. Vigara, J. Soriano-Lopez,
J. R. Galan-Mascaros, Inorg. Chem. 2012, 51, 11707.
b) M. Craven, R. Yahya, E. Kozhevnikova, R. Boomishankar,
C. M. Robertson, A. Steiner, I. Kozhevnikov, Chem. Commun.
2013, 49, 349. c) L. Yu, Y. Ding, M. Deng, Appl. Catal. Environ.
2017, 209, 45. d) R. Kaushik, R. Sakla, D. A. Jose, A. Ghosh,
New J. Chem. 2020, 44, 3764.
[2] a) J. Du, Z. L. Lang, Y. Y. Ma, H. Q. Tan, B. L. Liu,
Y. H. Wang, Z. H. Kang, Y. G. Li, Chem. Sci. 2020, 11, 3007.
b) L. H. Lin, L. Y. Gao, K. Xie, R. Jiang, S. Lin, Phys. Chem.
Chem. Phys. 2020, 22, 7234. c) X. R. Tian, Y. Q. Zhang,
Y. Y. Ma, Q. Zhao, Z. G. Han, Catal. Sci. Techol. 2020, 10,
2593.
[14] a) G. Grover, R. Nath, R. Bhatia, M. J. Akhtar, Bioorg. Med.
Chem. 2020, 28, 115585. (b) M. Henary, C. Kananda, L. Rotolo,
B. Savino, E. A. Owens, G. Cravotto, RSC Adv. 2020, 10, 14170.
c) Z. X. Du, J. X. Li, Inorg. Chim. Acta 2015, 436, 159.
d) J. X. Li, Z. X. Du, L. L. Zhang, D. L. Liu, Q. Y. Pan, Inorg.
Chim. Acta 2020, 512, 119890. e) R. Sreedevi, S. Saranya,
G. Anilkumar, Adv. Synth. Catal. 2019, 361, 4625. f) J. X. Li,
Z. X. Du, Q. Y. Pan, L. L. Zhang, D. L. Liu, Inorg. Chim. Acta
2020, 509, 119677.
[15] S. S. Gholap, Eur. J. Med. Chem. 2016, 110, 13.
[16] D. Mori, Y. Kimura, S. Kitamura, Y. Sakagami, Y. Yoshioka,
T. Shintani, T. Okamoto, M. Ojika, J. Org. Chem. 2007, 72, 7190.
[17] S. B. Singh, M. A. Goetz, E. T. Jones, G. F. Bills,
R. A. Giacobbe, L. Herranz, S. Stevensmiles, D. L. Williams,
J. Org. Chem. 1995, 60, 7040.
[3] S. Hosseinzadeh-Baghan, M. Mirzaei, H. Eshtiagh-Hosseini,
V. Zadsirjan, M. M. Heravi, J. T. Mague, Appl. Organomet.
Chem. 2020, 34, e5793.
[18] J. Kobayashi, M. Sekiguchi, H. Shigemori, A. Ohsaki, Tetrahe-
dron Lett. 2000, 41, 2939.
[4] a) L. L. Xu, Y. H. Wang, X. Yang, X. D. Yu, Y. H. Guo,
J. H. Clark, Green Chem. 2008, 10, 746. b) W. L. Xie, F. Wan,
Chem. Eng. J. 2019, 365, 40.
[5] S. Berardi, M. Carraro, M. Iglesias, A. Sartorel, G. Scorrano,
M. Albrecht, M. Bonchio, Chem. – Eur. J. 2010, 16, 10662.
[6] a) M. Nyman, P. C. Burns, Chem. Soc. Rev. 2012, 41, 7354.
b) M. Mirzaei, H. Eshtiagh-Hosseini, M. Alipour, A. Frontera,
Coord. Chem. Rev. 2014, 275, 1. c) S. Taleghani, M. Mirzaei,
H. Eshtiagh-Hosseini, A. Frontera, Coord. Chem. Rev. 2016,
309, 84.
[19] C. Osterhage, R. Kaminsky, G. M. Konig, A. D. Wright, J. Org.
Chem. 2000, 65, 6412.
[20] Z. Q. Feng, F. M. Chu, Z. R. Guo, P. Y. Sun, Bioorg. Med.
Chem. Lett. 2009, 19, 2270.
[21] C. Peifer, R. Selig, K. Kinkel, D. Ott, F. Totzke, C. Schachtele,
R. Heidenreich, M. Rocken, D. Schollmeyer, S. Laufer, J. Med.
Chem. 2008, 51, 3814.
[22] T. Kawasuji, M. Fuji, T. Yoshinaga, A. Sato, T. Fujiwara,
R. Kiyama, Bioorg. Med. Chem. 2007, 15, 5487.
[7] a) M. Fallah, S. Sohrabnezhad, M. Abedini, Appl. Organomet.
Chem. 2019, 33, e4801. b) S. S. Li, J. P. Pan, X. X. Wu,
Y. H. Fu, Q. Xiao, F. M. Zhang, W. D. Zhu, Appl. Organomet.
Chem. 2019, 33, e5233. c) R. A, Z. Rather, N. Siddiqui, Appl.
Organomet. Chem. 2019, 33, e5176. d) L. X. Bao, Z. B. Yu,
T. Fei, Z. Y. Yan, J. Z. Zli, C. H. Sun, S. P. Pang, Appl.
Organomet. Chem. 2020, 34, e5607. e) X. J. Li, Z. H. Zhou,
Y. Z. Zhao, D. Ramella, Y. Luan, Appl. Organomet. Chem.
2020, 34, e5445. f) N. Nagarjun, P. Concepcion,
A. Dhakshinamoorthy, Appl. Organomet. Chem. 2020, 34,
e5578. g) E. Niknam, F. Panahi, A. Khalafi-Nezhad, Appl.
Organomet. Chem. 2020, 34, e5470. h) M. Torkzadeh-Mahani,
M. Zaboli, M. Barani, M. Torkzadeh-Mahani, Appl.
Organomet. Chem. 2020, 34, e5581. i) A. Dhakshinamoorthy,
S. Navalon, A. M. Asiri, H. Garcia, Chem. Commun. 2020, 56,
26. j) G. Gao, J. Q. Di, H. Y. Zhang, L. P. Mo, Z. H. Zhang,
J. Catal. 2020, 387, 39. k) J. N. Zhang, X. H. Yang, W. J. Guo,
B. Wang, Z. H. Zhang, Synlett 2017, 28, 734.
[8] M. Ghahramaninezhad, B. Soleimani, M. N. Shahrak, New
J. Chem. 2018, 42, 4639.
[9] Y. W. Liu, X. Yang, J. Miao, Q. Tang, S. M. Liu, Z. Shi,
S. X. Liu, Chem. Commun. 2014, 50, 10023.
[10] E. Rafiee, N. Nobakht, L. Behbood, Res. Chem. Intermed. 2017,
43, 951.
[11] W. T. Xu, X. K. Pei, C. S. Diercks, H. Lyu, Z. Ji, O. M. Yaghi,
J. Am. Chem. Soc. 2019, 141, 17522.
[23] M. Cho, E. Choi, J. S. Yang, C. Lee, J. J. Seo, B. S. Kim,
S. J. Oh, H. M. Kim, K. Lee, S. K. Park, H. J. Kwon, G. Han,
ChemMedChem 2013, 8, 272.
[24] C. L. Zhuang, Z. Y. Miao, L. J. Zhu, G. Q. Dong, Z. Z. Guo,
S. Z. Wang, Y. Q. Zhang, Y. L. Wu, J. Z. Yao, C. Q. Sheng,
W. N. Zhang, J. Med. Chem. 2012, 55, 9630.
[25] S. S. Zimmerman, A. Khatri, E. C. Garnier-Amblard,
P. Mullasseril, N. L. Kurtkaya, S. Gyoneva, K. B. Hansen,
S. F. Traynelis, D. C. Liotta, J. Med. Chem. 2014, 57, 2334.
[26] D. N. Yang, C. H. Huang, H. Liao, H. W. Zhang, S. Y. Wu,
Q. H. Zhu, Z. Z. Zhou, ACS Omega 2019, 4, 17556.
[27] a) M. Ergun, C. Dengiz, M. S. Ozer, E. Sahin, M. Balci, Tetra-
hedron 2014, 70, 5993. b) M. D. Clift, R. J. Thomson, J. Am.
Chem. Soc. 2009, 131, 14579. c) T. Terauchi, T. Kamikawai,
M. G. Vinogradov, E. V. Starodubtseva, M. Takeda,
M. Kainosho, Org. Lett. 2011, 13, 161.
[28] a) J. G. Greger, S. J. P. Yoon-Miller, N. R. Bechtold,
S. A. Flewelling, J. P. MacDonald, C. R. Downey, E. A. Cohen,
E. T. Pelkey, J. Org. Chem. 2011, 76, 8203. b) M. Vorona,
N. Orlova, E. Kuznetsov, S. Vikainis, E. Liepinsh, S. Belyakov,
A. Mishnev, G. Veinberg, Chem. Heterocy. Comp. 2013, 49,
1118. c) R. Q. Ran, J. He, S. D. Xiu, K. B. Wang, C. Y. Li, Org.
Lett. 2014, 16, 3704. d) P. Mowery, F. B. Mejia,
C. L. Franceschi, M. H. Kean, D. O. Kwansare, M. M. Lafferty,
N. D. Neerukonda, C. E. Rolph, N. J. Truax, E. T. Pelkey, Bio-
org. Med. Chem. Lett. 2017, 27, 191. e) V. S. Barcelo, S. Bienz,
J. Org. Chem. 2018, 83, 2734. f) H. Ahankar, A. Ramazani,
K. Slepokura, T. Lis, V. Kinzhybalo, Res. Chem. Intermed.
2019, 45, 5007.
[12] X. Yu, L. Wang, S. M. Cohen, CrystEngComm 2017, 19, 4126.
[13] a) J. Y. Han, D. P. Wang, Y. H. Du, S. B. Xi, Z. Chen,
S. M. Yin, T. H. Zhou, R. Xu, Appl. Catal. A. Gen. 2016, 521,
83. b) W. A. Shah, A. Waseem, M. A. Nadeem, P. Kogerler,
Appl. Catal. A. Gen. 2018, 567, 132. c) M. Samaniyan,
M. Mirzaei, R. Khajavian, H. Eshtiagh-Hosseini, C. Streb, ACS
[29] a) M. N. Chen, L. P. Mo, Z. S. Cui, Z. H. Zhang, Curr.
Opin. Green. Sustain. Chem. 2019, 15, 27. b) H. Alinezhad,

14 of 14
BAO-LE ET AL.
M. Tarahomi, B. Maleki, A. Amiri, Appl. Organomet.
d) Y. Han, J. Q. Di, A. D. Zhao, Z. H. Zhang, Appl. Organomet.
Chem. 2019, 33, e5172.
[38] X. M. Zhang, Z. H. Zhang, B. H. Zhang, X. F. Yang, X. Chang,
Z. Zhou, D. H. Wang, M. H. Zhang, X. H. Bu, Appl Catal B
2019, 256, 117804.
Chem. 2019, 33, e4661. c) B. Maleki, M. Chahkandi,
R. Tayebee, S. Kahrobaei, H. Alinezhad, S. Hemmati, Appl.
Organomet. Chem. 2019, 33, e5118. d) M. Tarahomi,
H. Alinezhad, B. Maleki, Appl. Organomet. Chem. 2019, 33,
e5203.
e)
B.
Maleki,
N.
Nasiri,
R.
Tayebee,
[39] a) J. S. Qin, D. Y. Du, W. Guan, X. J. Bo, Y. F. Li, L. P. Guo,
Z. M. Su, Y. Y. Wang, Y. Q. Lan, H. C. Zhou, J. Am. Chem.
Soc. 2015, 137, 7169. b) N. L. Rosi, J. Eckert, M. Eddaoudi,
D. T. Vodak, J. Kim, M. O'Keeffe, O. M. Yaghi, Science 2003,
300, 1127. c) N. Ebrahimi, R. Fazaeli, H. Aliyan,
Z. Naturforsch. 2016, 71, 211. d) C. Y. Sun, S. X. Liu,
D. D. Liang, K. Z. Shao, Y. H. Ren, Z. M. Su, J. Am. Chem. Soc.
2009, 131, 1883.
A. Khojastehnezhad, H. A. Akhlaghi, RSC Adv. 2016, 6, 79128.
f) M. Zhang, Y. H. Liu, Z. R. Shang, H. C. Hu, Z. H. Zhang,
Cat. Com. 2017, 88, 39. g) M. Zhang, Q. Y. Fu, G. Gao,
H. Y. He, Y. Zhang, Y. S. Wu, Z. H. Zhang, ACS Sustainable
Chem. Eng. 2017, 5, 6175. h) G. Gao, P. Wang, P. Liu,
W. H. Zhang, L. P. Mo, Z. H. Zhang, Chin. J. Org. Chem.
2018, 38, 846.
[30] M. M. Khan, S. Khan, S. C. Sahoo, ChemistrySelect 2018, 3,
1371.
[31] R. Ghorbani-Vaghei, D. Azarifar, S. Dalirana, A. R. Oveisi,
RSC Adv. 2016, 6, 29182.
[32] L. Lv, S. Zheng, X. Cai, Z. Chen, Q. Zhu, S. Liu, ACS Comb.
Sci. 2013, 15, 183.
[33] H. Singh, J. K. Rajput, J. Mater. Sci. 2018, 53, 3163.
[34] A. T. Khan, A. Ghosh, M. M. Khan, Tetrahedron Lett. 2012, 53,
2622.
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Bao-Le L, Zhang H-Y,
Di J-Q, Zhang Z-H. Polyoxometalate immobilized
on MOF-5 as an environment-friendly catalyst for
the synthesis of poly-functionalized 3-pyrrolin-2-
ones. Appl Organomet Chem. 2020;e6064. https://
doi.org/10.1002/aoc.6064
[35] S. Rana, M. Brown, A. Dutta, A. Bhaumik, C. Mukhopadhyay,
Tetrahedron Lett. 2013, 54, 1371.
[36] B. B. F. Mirjalili, R. Z. Reshquiyea, RSC Adv. 2015, 5, 15566.
[37] a) M. Zhang, Y. Han, J. L. Niu, Z. H. Zhang, Adv. Synth. Catal.
2017, 359, 3618. b) Y. Han, M. Zhang, Y. Q. Zhang,
Z. H. Zhang, Green Chem. 2018, 20, 4891. c) M. Zhang,
M. N. Chen, Z. H. Zhang, Adv. Synth. Catal. 2019, 361, 5182.