A Thiophene-2-carboxamide-Functionalized Zr(IV) Organic Framework as a Prolific and Recyclable Heterogeneous Catalyst for Regioselective Ring Opening of Epoxides

Article abstract of DOI:10.1021/acs.inorgchem.9b02608

A new thiophene-2-carboxamide-functionalized Zr-UiO-66 MOF (1) was synthesized by employing a traditional solvothermal procedure. Compound 1 displayed high thermal (up to 340 °C under an Ar atmosphere) and chemical stability (in water, 1 M HCl, and acetic acid). A nitrogen physisorption measurement with the activated form of 1 (denoted 1) exhibited a BET surface area (781 m²/g) despite attachment of a bulky side chain with the linker molecule. Compound 1 was able to heterogeneously catalyze the ring-opening reaction of epoxides with amines. Catalyst 1 exhibited significant yields as well as wide substrate scope in the ring opening of epoxides by means of amines. It also displayed better catalytic performance in comparison to known MOF catalysts such as Cu₃(BTC)₂, Fe(BTC) (BTC: 1, 3, 5-benzenetricarboxylate), and Zr-UiO-66. Control experiments were performed with free linker, Zr(IV) salt and without catalyst 1, confirming the exclusive role of 1 in the catalytic reaction. The reusability characteristics of catalyst 1 was established for up to five consecutive catalytic cycles. The synthesis and characterization of the linker molecule, material 1, and 1 and mechanism of the catalysis reaction were studied elaborately.

Full text of DOI:10.1021/acs.inorgchem.9b02608

Article
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
A Thiophene-2-carboxamide-Functionalized Zr(IV) Organic
Framework as a Prolific and Recyclable Heterogeneous Catalyst for
Regioselective Ring Opening of Epoxides
Aniruddha Das,† Nagaraj Anbu,‡ Helge Reinsch,§ Amarajothi Dhakshinamoorthy,*,‡
and Shyam Biswas*,†
†Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, Assam 781039, India
‡School of Chemistry, Madurai Kamaraj University, Madurai, Tamil Nadu 625021, India
§Institut fu
̈
r Anorganische Chemie, Christian-Albrechts-Universitat, Max-Eyth-Strasse 2, 24118 Kiel, Germany
̈
S
* Supporting Information
ABSTRACT: A new thiophene-2-carboxamide-functionalized
Zr-UiO-66 MOF (1) was synthesized by employing a
traditional solvothermal procedure. Compound 1 displayed
high thermal (up to 340 °C under an Ar atmosphere) and
chemical stability (in water, 1 M HCl, and acetic acid). A
nitrogen physisorption measurement with the activated form
of 1 (denoted 1′) exhibited a BET surface area (781 m2/g)
despite attachment of a bulky side chain with the linker
molecule. Compound 1′ was able to heterogeneously catalyze
the ring-opening reaction of epoxides with amines. Catalyst 1′
exhibited significant yields as well as wide substrate scope in
the ring opening of epoxides by means of amines. It also
displayed better catalytic performance in comparison to
known MOF catalysts such as Cu3(BTC)2, Fe(BTC) (BTC:
1, 3, 5-benzenetricarboxylate), and Zr-UiO-66. Control experiments were performed with free linker, Zr(IV) salt and without
catalyst 1′, confirming the exclusive role of 1′ in the catalytic reaction. The reusability characteristics of catalyst 1′ was
established for up to five consecutive catalytic cycles. The synthesis and characterization of the linker molecule, material 1, and
1′ and mechanism of the catalysis reaction were studied elaborately.
Ring opening of oxiranes by nucleophilic attack of various
amines is the easiest way to prepare β-amino alcohols.7,22
However, this approach is not acceptable due to its
disadvantages such as the sluggish reaction rate because of
the sensitivity of epoxides and decrease in regioselectivity.
There are many reports involving the preparation of β-amino
alcohols utilizing epoxides as electrophiles.17,23−29 Researchers
have designed several routes such as the use of homogeneous
catalysts,30,31 alumina,1 alkali metals,32 metal amides,33 and
silica gel in order to increase the electrophilicity of epoxides.
Unfortunately, most of these methods have several drawbacks
such as the moisture-sensitive character of the catalysts, the
low efficiency of catalysts, long reaction time, less regiose-
lectivity, high reaction temperature and pressure, poor yield
and recyclability, etc.1,4,22,34−36
INTRODUCTION
■
Epoxides are considered to be privileged molecules in organic
chemistry because of their versatile nucleophilic opening
character, producing 1,2-difunctionalized structures, and also
because such cleavages often occur with trans stereo-
chemistry.1−4 In the field of asymmetric catalysis, β-amino
alcohols are significant as chiral ligands and chiral auxiliaries
mostly originating from nature.5−9 Amino alcohols are often
derivatized to increase their chelating abilities or steric
influences.10,11 In the fields of synthetic organic chemistry,
biological chemistry, and medicinal industry, β-amino alcohols
have occupied a dominant position because they are used as
building units for therapeutic agents, insecticidal agents, β-
blockers, antimalarial agents, and numerous biologically active
natural products.12−17 Cyclic amino alcohols such as quinines
are a class of naturally occurring, biologically active products
that are required in the treatment of malaria.18 Renin and HIV-
1 protein inhibitors constitute pharmacologically active amino
alcohols, and one such example is saquinavir.18 Often, β-
adrenergic blockers, which constitute a class of β-amino
alcohols, are used to regulate cardiovascular diseases such as
hypertension, cardiac arrhythmias, and angina pectoris.18−21
Three-dimensional (3D) metal-organic frameworks
(MOFs) , being stable, very crystalline solid porous
compounds, have attracted much scientific interest for gas
adsorption and separation,37−39 heterogeneous catalysis of
Received: August 30, 2019
© XXXX American Chemical Society
A
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the products was carried out by using GC-MS and 1H NMR
techniques (Figures S12−S49 in the Supporting Information). At the
end of the reaction, diluting of the mixture, washing the catalyst with
dichloromethane (2 × 5 mL), and drying (at 80 °C for 45 min) were
carried out consecutively. The recovered catalyst was used in the next
cycle with new substrates. Each cycle followed the same procedure for
catalyst recycling.
numerous organic reactions,40−43 sensing,44−47 photonic
applications,46 drug delivery,48 proton conductivity,49 etc.
Moreover, porous MOFs have shown considerable heteroge-
neous catalytic activities in many organic reactions because of
their insoluble character, exceptionally large surface area,40
tunable pore size,50 adjustable internal surface properties, and
easy separation of the catalyst after reaction.51 In this regard,
Zr-MOFs possessing exceptional thermal as well as high
chemical stabilities are considered as remarkable candidates for
various heterogeneous catalysis reactions.34,52−57 Synthetically,
new MOFs with desirable structures and specific properties
can be designed and synthesized by tuning the side functional
groups of linker molecules. In case of epoxide ring-opening
reactions by means of amines, those catalysts are preferred,
which enhance the electrophilic character of epoxides or
increase the nucleophilic character of amines.
RESULTS AND DISCUSSION
■
Preparation. Different possible reactions were carried out
using ZrCl4 and the H2BDC-C5H4NOS linker in DMF at
Keeping in mind all the factors mentioned above, we have
designed a new Zr(IV)-based UiO-66 compound having a
thiophene-2-carboxamide side functional moiety attached
with the linker molecule. We have explored the heterogeneous
catalytic activity of this compound in the ring-opening
reactions of epoxides by amines. The Zr-UiO-66 compound
with a thiophene-2-carboxamido functionality was synthesized
solvothermally and systematically characterized. The com-
pound showed thermal stability and chemical stability toward
water and acids (acetic acid and 1 M HCl). Compound 1′ can
be considered as a porous material due to its large BET surface
area (781 m2/g). The catalytic performances of 1′ are
outstanding in terms of remarkable yield, purity and
regioselecivity of products, size selectivity of substrates, and
reusability of the catalyst.
Figure 1. PXRD patterns of (a) Zr(IV)-based UiO-66 (theoretical),
(b) 1 (experimental), and (c) 1′ (experimental).
EXPERIMENTAL SECTION
■
Synthesis of [Zr6O4(OH)4(BDC-C5H4NOS)6]·4.5H2O·3.5DMF
(Zr-UiO-66-thiophene-2-carboxamido, 1). ZrCl4 (32 mg, 0.14
mmol) and 2-(thiophene-2-carboxamido)benzene-1,4-dicarboxylic
acid linker (H2BDC-C5H4NOS; 40 mg, 0.14 mmol) were placed in
a glass tube in a 1:1 molar ratio. N,N-Dimethylformamide (DMF; 2
mL) and formic acid (572 μL, 4.55 mmol) were poured into the glass
tube holding the reaction mixture. Afterward, the glass tube was
placed onto a block heater which was maintained at 120 °C for 1 day.
After 1 day, a white precipitate was collected by vacuum filtration,
followed by washing with acetone. For drying purposes, the powder
sample was kept inside an oven at 80 °C for 4 h. The yield calculated
considering the zirconium salt was 58 mg (0.02 mmol, 92%). Anal.
Calcd for C88.5H85.5N9.5O46S6Zr6 (2757.90 g mol−1): C, 38.54; H,
3.12; N, 4.82. Found: C, 38.41; H, 2.63; N, 4.73%. FT-IR (KBr,
cm−1): 3436 (br), 1646 (s), 1582 (s), 1509 (w), 1423 (vs), 1380 (vs),
1306 (s), 1258 (s), 1170 (w), 1110 (w), 1070 (w), 858 (w), 767 (vs),
738 (w), 662 (vs), 596 (w), 542 (w), 481 (s).
different temperatures using four modulators (benzoic acid,
acetic acid, trifluoroacetic acid, and formic acid).58,59 A highly
crystalline sample of 1 was achieved when a mixture of ZrCl4,
H2BDC-C5H4NOS linker, formic acid, and DMF in the
required molar ratio was subjected to a solvothermal reaction
at 120 °C for 1 day.
FT-IR Study. The IR spectra of 1 and 1′ were recorded to
confirm the presence of the linker molecule in the compounds.
As described in Figure S4 in the Supporting Information, the
very strong peak at 1586 cm−1 is due to an asymmetric
stretching vibration and the strong peak at 1423 cm−1 is due to
the presence of a symmetric stretching vibration of carboxylate
linker molecules. Therefore, these results ensure the existence
of the linker molecules within the frameworks of 1 and 1′.60,61
In the spectrum of the free linker molecule, the peak at 1654
cm−1 is attributed to the carbonyl group from the amide
moiety.62 This peak was shifted to 1647 cm−1 for both 1 and
1′, indicating the incorporation of the amide linkage within the
framework of the MOF.
PXRD Analysis. Figure 1 shows the PXRD patterns of 1
and 1′. From the PXRD patterns, it is obvious that both
compounds have the same peak intensity as well as the same
peak positions as the theoretical peak pattern of the analogous
UiO-66 compound.63,64 Therefore, it is concluded that 1 has a
UiO-66 framework topology. From Figure 1, it is also
concluded that 1 is robust enough toward the activation
conditions and the activated compound also has the UiO-66
framework.63−65
Activation of Compound 1. Activation of compound 1 was
carried out in two stages. In the first stage, 100 mg of compound 1
was dispersed in methanol (25 mL) and stirring was conducted at
room temperature for 1 day. Later, the solvent was removed by
filtration and drying of the precipitate was executed inside an oven at
70 °C for 4 h. Finally, the solid powder was placed in a sealed
activation tube, which was degassed for 1 day at 130 °C to achieve the
activated sample, denoted 1′.
Reaction Procedure. In a typical reaction, substrate 1 (0.6
mmol) and substrate 2 (0.5 mmol) were placed in a reaction vessel
containing 15 mg of catalyst. Then, this mixture was mixed
thoroughly and kept for 12 h under ambient conditions. The progress
of the ring opening of epoxide reaction with respect to time was
monitored by gas chromatography (GC) through sampling of aliquots
at various time intervals. GC was utilized to access the yield of the
final product by means of internal standard method. Identification of
B
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Scheme 1. Reaction Scheme for the Ring Opening of Substrate 1 by Substrate 2 Using 1′ as a Heterogeneous Catalyst
Table 1. Optimization of Reaction Parameters for the Ring
Opening of Substrate 1 by Substrate 2 Employing 1′ as a
a
Heterogeneous Catalyst
c
selectivity (%)
b
entry
solvent
yield (%)
3
4
1
2
3
4
5
6
7
ACN
THF
DCM
benzene
toluene
44
23
54
51
67
95
96
87
93
94
95
4
13
7
6
5
96
100
4
d
2
a
Reaction conditions unless specified otherwise: substrate 1 (0.6
mmol), substrate 2 (0.5 mmol), solvent (1 mL), catalyst 1′ (15 mg),
b
room temperature, 12 h. Determined by GC using an internal
c
d
standard method. Determined by GC and GC-MS. In the absence
of catalyst 1′.
Figure 3. Time−yield plot for ring opening of substrate 1 by substrate
2 using 1′ as a heterogeneous solid catalyst: (a) with catalyst; (b) with
filtering of the catalyst after 1 h; (c) without catalyst. Reaction
conditions: substrate 1 (0.6 mmol), substrate 2 (0.5 mmol), toluene
(1 mL), 1′ (15 mg), room temperature, 12 h.
Figure 2. Effect of catalyst loading for the aminolysis of 1 by 2 in the
presence of (a) 5 mg, (b) 10 mg, and (c) 15 mg of 1′. Standard
deviation analysis was performed by measuring four individual
experiments for each catalyst loading.
Structure Description. The UiO-66 MOF with a Zr(IV)
ion was discovered by Lillerud’s group in 2008.64 As
demonstrated by Lillerud’s group, the Zr-UiO-66 framework
is composed of [Zr6O4(OH)4]12+ clusters in which every
Zr(IV) ion is octacoordinated (square-antiprismatic geome-
try). 1,4-Benzenedicarboxylate (BDC) linker molecules inter-
connect one SBU with another one in the framework. A 3D
cubic framework is obtained by interconnecting Zr6 clusters
with BDC linkers (12 linkers per cluster). The 3D framework
possesses larger octahedral and smaller tetrahedral cages.
Narrow triangular windows connect the two types of cages. For
the present MOF (Figure S5 in the Supporting Information),
Figure 4. Reusability plot for ring opening of substrate 1 by substrate
2 using 1′ as a solid catalyst.
thiophene-2-carboxamide-functionalized BDC plays a role
similar to that played by unfunctionalized BDC in the
formation of the UiO-66 framework.64,65 Figure S6 in the
Supporting Information shows the pore size distribution plot
for 1′. This plot confirms that the microspores of 1′ are
centered at 15.2 Å.
For structural analysis, the PXRD pattern of 1 was indexed.
The derived lattice parameters are compared with those of the
C
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Figure 7. Time−yield plot for ring opening of substrate 1 by substrate
2 using different MOFs as solid heterogeneous catalysts: (a)
Cu3(BTC)2; (b) Zr-UiO-66; (c) Fe(BTC); (d) 1′.
Figure 5. Comparison of the PXRD pattern of a fresh sample of 1′ (a)
with that of the same sample recovered after the first (b) and fifth (c)
cycles of catalysis.
Figure 8. Time−yield plots for the aminolysis of substrate 1 by
■
Figure 6. Time−yield plot for the ring opening of substrate 1 by
substrate 2 using 1′ (a) and its corresponding homogeneous
counterparts metal salt (ZrCl4) (b) and linker (H2BDC-(thiophene-
2-carboxamido)) (c).
substrate 2 using different solid heterogeneous catalysts: ( ) MIL-
⧫
●
▲
▼
53(Al); ( ) neutral Al2O3; ( ) SiO2; ( ) 1′; ( ) K10
montmorillonite clay.
the resulting model represents the pseudorhombohedral
setting of the cubic unit cell with identical cell edges and all
angles fixed to 60°. However, due to the attached functional
groups, the actual symmetry of such a model is only triclinic
P1. Thus, we modeled the structure of 1 starting with the
reported model for UiO-66-CO2H in triclinic symmetry, using
the Materials Studio software suite.67 Starting with the
literature values for the unit cell parameters (a = b = c =
14.7106 Å, α = β = γ = 60°) of UiO-66-CO2H, we deduced the
values for 1 by Pawley refinement to be a = b = c = 14.7174 Å
with angles fixed to 60°. After these cell parameters were
imposed, the functional −CO2H groups were replaced by
thiophene-2-carboxamide moieties. Eventually, protons were
added to the linker molecules and the model was fully relaxed
by force-field calculations using the universal fore field UFF.68
The calculated PXRD pattern for this resulting final model is in
close agreement with the experimental data, as shown in Figure
reported unfunctionalized Zr-UiO-66 MOF in Table S1 in the
Supporting Information.59,63 The similarities in lattice
parameters indicate that the structure of 1 is cubic and
possesses a UiO-66 framework topology.59,63 The structural
similarity of 1 with Zr-UiO-66 was further confirmed by
Pawley refinement (Figure S7 in the Supporting Information)
with the PXRD pattern of 1.
As indicated by indexing and Pawley refinement, the
structure of 1 exhibits a cubic symmetry like the parent
framework of UiO-66. This also means that the attached
functional groups are fully distributed over different possible
positions. Due to this inherent configurational and conforma-
tional disorder, the localization of the attached moieties by the
Rietveld method is impossible. However, the structure of such
variants of UiO-66 can be well modeled in a lower symmetry,
as described for example, for UiO-66-CO2H.66 In such cases,
D
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Figure 9. Stacked 1H NMR spectra of substrate 1, the linker, and a physical mixture of linker and substrate 1 at different time intervals in DMSO-
d6.
S8 in the Supporting Information. The crystallographic
information file is linked at the end of this paper.
Supporting Information. From this physisorption analysis, the
surface area and micropore volume of the material were
derived as 781 m2/g and 0.44 cm3/g at a p/p0 value of 0.5,
respectively. The shape of the N2 sorption curves and the value
of the pore volume revealed that 1′ is a microporous material.
Compound 1′ is comparable with the reported parent and
functionalized UiO-66 MOF with regard to surface area and
micropore volume.59,70,71
Thermal Stability. The thermal stability of 1 and 1' was
determined by performing thermogravimetric (TG) experi-
ments under argon atmosphere. From Figure S9 in the
Supporting Information, it is inferred that both 1 and 1′ are
stable up to 340 °C. The existing UiO-66 type MOFs have
shown thermal stability similar to that of 1.69,70
Catalytic Activity. The catalytic performance of 1′ was
investigated in the aminolysis of epoxides. Styrene oxide
(substrate 1) and aniline (substrate 2) were chosen as
representative substrates. This reaction afforded two re-
gioisomers, and they are shown in Scheme 1 as products 3
and 4. The achieved results are provided in Table 1. The
analysis of the observed products was executed by GC-MS and
1H NMR methods (Figures S12−S49 in the Supporting
Information). The ring-opening reaction between 1 and 2
using 1′ as a catalyst in various solvents such as ACN
(acetonitrile), THF (tetrahydrofuran), DCM (dichlorome-
thane), benzene, and toluene exhibited moderate yields
between 23 and 67% after stirring for 12 h at ambient
temperature (Table 1, entries 1−5). In contrast, the reaction of
1 and 2 with 1′ as a solid catalyst afforded 95% yield under
solvent-free conditions at ambient temperature after 12 h
(Table 1, entry 6). In contrast, only 2% conversion was
obtained under identical conditions when a control experiment
was conducted in the absence of catalyst (Table 1, entry 7). In
all of these cases, the use of 1′ as a solid catalyst showed the
formation of 3 as the major product. These experiments clearly
suggest that the reaction is promoted solely by 1′ as a catalyst
in affording 3 as the major product. Then, the next logical
move was to investigate the influence of catalyst loading of this
reaction under identical conditions. Figure 2 provides the
time−yield profile for the ring-opening reaction of substrate 1
by substrate 2 to obtain the desired product 3 by observing
enhancement in the initial reaction rate as a function of catalyst
From Figure S9, it is noted that there are distinct weight loss
stages for 1. In the temperature range of 25−150 °C, there was
the first weight loss of 2.9 wt % (calcd 2.9 wt %) due to the loss
of 4.5 water molecules. The second weight loss was found to
be 9.2 wt % (calcd 9.3 wt %) due to the loss of 3.5 DMF
molecules. The linker molecules start to be eliminated from the
framework of 1 beyond 340 °C. Therefore, it is confirmed that
1 is stable up to 340 °C. The desolvated sample (1′) adsorbs
moisture when it is stored in an air atmosphere. As a result, it
shows a weight loss of 2.7 wt % in the region of 25−150 °C for
the removal of adsorbed water molecules.
Chemical Stability. Chemical stability is one of the
important factors which is crucial for the practical application
of a MOF. The chemical stability of 1′ was ascertained by
treating with water, 1 M HCl, glacial acetic acid, and 0.01 M
NaOH solutions for 14 h. Subsequently, the solid residues
were obtained by filtration and they were placed in an oven
maintained at 100 °C for 6 h. PXRD patterns were collected
with the dry solids. Although the structural integrity of 1′ was
lost upon treatment with 0.01 M NaOH solution, it remained
stable in water, 1 M HCl, and glacial acetic acid, as evidenced
by PXRD patterns (Figure S10 in the Supporting Information).
These results point out that the chemical stability of 1′ is quite
satisfactory and is comparable with that of the previously
reported UiO-66 MOFs.59,70
N2 Sorption Study. The activated compound 1′ was used
to carry out N2 physisorption analysis. The obtained type I
type N2 sorption isotherms are shown in Figure S11 in the
E
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Table 2. Ring Opening of Substrate 1 by Various Aryl and
Table 3. Ring Opening of Other Epoxide Substrates by
a
Alkyl Amine Substrates Using 1′ as a Solid Heterogeneous
Substrate 2 Using 1′ as a Heterogeneous Solid Catalyst
a
Catalyst
a
Reaction conditions unless specified otherwise: epoxide (0.6 mmol),
substrate 2 (0.5 mmol), catalyst 1′ (15 mg), room temperature, 12 h.
b
c
Determined by GC using an internal standard method. Determined
d
by GC and GC-MS. At 60 °C.
inherently heterogeneous in nature, the catalyst was taken out
from reaction mixture after 1 h when the conversion of 1 was
about 18%. Then, the reaction in the absence of 1′ was
continued under identical experimental conditions for the
remaining time (Figure 3). The observed results suggest that
the rate of reaction became completely constant after
elimination of the catalyst from the reaction vessel. Further,
the filtrate of the reaction mixture was investigated by ICP-
AES, which verified the absence of zirconium (below the
detection limit). These results convincingly demonstrate that
the reaction is heterogeneous in nature. Moreover, the catalyst
was conveniently retrieved from the reaction mixture by
filtration and used for five cycles without any decay in its
catalytic performance (Figure 4). The five-time used catalyst
showed a crystalline pattern (Figure 5) identical with that of
the fresh solid through PXRD analysis (Figure 5), thus
verifying the structural integrity of 1′ under the reaction
conditions. Moreover, the crystalline nature of 1′ was verified
by FE-SEM analysis (Figures S50 and S51 in the Supporting
Information) and an unaltered morphology of 1′ after catalysis
was observed in comparison to its fresh sample. In addition,
EDX elemental analysis and EDX mapping revealed no
changes in the elemental composition of 1′ before and after
catalysis, as shown in Figures S52−S55 in the Supporting
Information.
The nature of active sites was also examined in 1′ by
comparing its activity with those of corresponding metal salt
and linker. The results achieved are displayed in Figure 6. The
activity of 1′ is significantly higher in comparison to ZrCl4
(metal component) and 2-(thiophene-2-carboxamido)-
benzene-1,4-dicarboxylic acid (linker). This may be attributed
to the presence of dual active sites in 1′ through the metal
node (Lewis acidic site) and the 2-(thiophene-2-carboxamido)
functionalized linker (pseudo Lewis acidic site) for the ring
opening of 1. This hypothesis was verified by conducting a
masking experiment with pyridine. The activities of ZrCl4,
linker, and 1′ were completely quenched by the introduction
of pyridine to the reaction mixture. These results unambigu-
ously prove that pyridine behaves as a Lewis base by
coordinating strongly to the metal ion like a σ bond, thus
inhibiting the interactions of substrate 1 with the metal
centers.72 Furthermore, the activities of 1′ and linker were
quenched by pyridine due to the formation of hydrogen
bonding between the −NH group of linker and N atom of
pyridine.73
a
Reaction conditions unless specified otherwise: substrate 1 (0.6
mmol), amine (0.5 mmol), catalysts 1′ (15 mg), room temperatue, 12
b
h. Determined by GC using an internal standard method.
c
d
e
Determined by GC and GC-MS. At 60 °C for 24 h. At 60 °C
for 12 h.
loading. This observation is due to the availability of a high
population of active sites with higher catalyst loading.
Figure 3 presents a time−yield profile for the conversion of
1 to 3 and 4 by 2 using 1′ as a solid catalyst and a control
experiment without 1′ in toluene at room temperature. These
catalytic results suggest that the presence of a catalyst is
required for this reaction even in the presence of solvents.
Further, to validate whether the present catalytic method is
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Scheme 2. Possible Mechanism for the Ring Opening of Substrate 1 by Substrate 2 through (a) Metal Sites (Zr4+) and (b)
Thiophene-2-carboxamido Linker in 1′
The activity of 1′ was also screened with a series of MOFs
possessing Lewis acidic sites such as Fe(BTC), Cu3(BTC)2,
and Zr-UiO-66, and the observed results are shown in Figure
7. These data prove that 1′ has better catalytic performance in
comparison to other tested MOFs under identical conditions.
This superior performance of 1′ could be due to the high
population of active sites in comparison to the other catalysts.
Interestingly, the enhanced catalytic performance of 1′ in
comparison to Zr-UiO-66 is due to the operation of dual active
sites in 1′.
In addition to comparing the activity of 1′ with other related
MOFs, the catalytic performance of 1′ was also compared with
some of the conventional catalysts such as MIL-53(Al), neutral
Al2O3, SiO2, and K10 montmorillonite clay employed for the
ring opening of epoxides by amines under similar conditions.
The observed catalytic data are given in Figure 8. K10
montmorillonite clay provided slightly higher activity than 1′,
but this activity difference is due to the difference in the
structure and active sites. Furthermore, the reactants reach the
active sites without having any diffusion limitation in clay,
while the use of 1′ impedes the diffusion of reactants. On other
G
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hand, the activity of 1′ was comparable to that of SiO2, while
the activities of Al2O3 and MIL-53(Al) were significantly lower
in comparison to 1′. Hence, it is very difficult to compare the
activity of 1′ with those of other conventional catalysts, since
the activity of a solid depends on many factors such as
structure of the catalyst, active sites, diffusion limitation, and
others. The activity of 1′ may be higher or lower in comparison
to conventional catalysts, but the objective of this work is not
to rank the present catalyst in the series but rather to
demonstrate the ability of 1′ to promote the ring opening of
epoxides by amines.
In order to enlarge the scope of our catalyst, aminolysis of
epoxides was performed with various amine substrates
catalyzed by 1′ using the optimized reaction parameters. The
obtained catalytic results are presented in Table 2. The
reaction of 1 with 2 in the presence of 1′ afforded a 95% yield
with the β-amino alcohol as the major regioisomer (Table 2,
entry 1). Similarly, 4- and 2-methylanilines were reacted
effectively with 1 to provide the respective products in 95%
yields under identical conditions (Table 2, entries 2 and 3).
Further, the aminolysis reaction of 1 by 4- and 2-methoxyani-
lines showed 94 and 95% yields, respectively, showing an
isomer identical with that of aniline (Table 2, entries 4 and 5).
In addition, the reaction of 1 with 4-chloro- and 4-
bromoanilines exhibited the corresponding β-amino alcohols
in 95 and 94% yields, respectively, under the optimized
reaction conditions (Table 2, entries 6 and 7). On the other
side, the aminolysis of 1 by 4-nitroaniline showed a 31% yield
at room temperature after 12 h, whereas the yield increased to
89% at 60 °C after 24 h (Table 2, entry 8). This decreased rate
with 4-nitroaniline may be due to the poor nucleophilic
character of the amino group caused by the existence of an
electron-withdrawing nitro group. A similar behavior was also
witnessed for the aminolysis reaction between 1 and 4-
aminobenzoic acid (Table 2, entry 9). In addition, the reaction
between 3-cyanoaniline and 1 with 1′ as a solid catalyst
exhibited an 82% yield at ambient temperature and a 93% yield
at 60 °C after 12 h (Table 2, entry 10).
Furthermore, the reaction of 1 and aminocyclohexane using
1′ as a solid catalyst afforded the secondary alcohol (isomer
II) as the major product at room temperature; however, the
yield increased to 92% at 60 °C after 12 h (Table 2, entry 11).
This inverse selectivity may be due to the steric hindrance of
the cyclohexane ring which prefers to attack the methylene
carbon in 1. Interestingly, the aminolysis reaction of 1 and n-
butylamine exhibited an equal ratio of regioisomers either at
room temperature or at 60 °C (Table 2, entry 12).
Furthermore, ring opening of other epoxide substrates with
2 using 1′ as a catalyst was also tested under identical
conditions. The obtained results are presented in Table 3. The
reaction of cyclohexene oxide with 2 in the presence of 1′
afforded a single product in 97% yield at ambient temperature
(Table 3, entry 1). Further, the aminolysis of epichlorohydrin
with 2 using 1′ as a solid catalyst showed the secondary alcohol
as the only product (Table 3, entry 2). This may be explained
due to the steric nature of the chlorine atom. Finally, mixtures
of regioisomers with equal selectivity were obtained for the
reaction between isobutylene oxide and substrate 2 with 1′ as a
catalyst at room temperature or at 60 °C (Table 3, entry 3).
A suitable reaction mechanism is proposed for the
aminolysis of substrate 1 by substrate 2 with 1′ as a solid
catalyst (Scheme 2). As discussed earlier, there are two types of
active sites in 1′: namely, the metal sites (Zr4+) and the linker.
Hence, the mechanism is proposed by involving both active
sites. Scheme 2a shows the interaction of substrate 1 with 1′
through oxygen by decreasing the electron density in the
carbon attached to phenyl, thus favoring nucleophilic attack.
This carbon site was attacked by 2 to give the expected
product 3. This mechanism is in agreement with earlier
literature reports involving metal sites as active sites.74−77
On the other hand, Scheme 2b provides the possible
mechanism through the linker installed in 1′. The interaction
of substrate 1 with catalyst 1′ occurs through the weak
coordination of an oxygen atom of substrate 1 with the N−H
and thiophene moieties in 1′. This interaction decreases the
electron density at the secondary carbon in substrate 1, thus
favoring the nucleophilic attack by substrate 2 to provide an
intermediate as shown in Scheme 2b. This further rearranges
to provide the expected product in a major proportion.
Furthermore, the formation of another product is also possible
through the attack of a nucleophile (substrate 2) at the
methylene carbon under identical reaction conditions.
One of the proposed intermediates in Scheme 2b is the
interaction of substrate 1 through the oxygen with 1′ of an N−
1
H bond. In order to prove this interaction, H NMR spectra
were recorded for the linker, substrate 1, and a physical
mixture of the linker with substrate 1. The observed results are
shown in Figure 9. The N−H proton in the linker is seen at
12.08 ppm, while upon addition of substrate 1, this peak was
shifted to downfield to 12.14 ppm after 10 min and further to
12.30 and 12.29 ppm after 1 and 8 h, respectively. These
results are in close agreement with an earlier report.78
Furthermore, an additional control experiment was performed
to prove the proposed mechanism with deuterated methanol
(CD3OD) as a nucleophile for the ring opening of substrate 1
under similar experimental conditions. The analysis of the
reaction mixture by GC-MS clearly indicates the formation of a
product with an m/z value of 156 (Figure S56 in the
Supporting Information), whereas the m/z value is 152 for
CH3OH (Figure S57 in the Supporting Information). These
experiments confirm that the hydrogen transfer occurring from
the protonated intermediate to the final product originates
from the nucleophile, as shown in Scheme 2.
CONCLUSIONS
■
We have demonstrated the synthesis and characterization of
the new 2-(thiophene-2-carboxamido)benzene-1,4-dicarbox-
ylic acid linker and successfully utilized it for the synthesis of
a Zr(IV)-based UiO-66 MOF. The MOF was synthesized
using a traditional solvothermal method and characterized
using PXRD, FT-IR, TG, and BET analysis. The specific BET
surface area of 1′ derived from nitrogen physisorption
experiment was 781 m2/g. The material showed high chemical
stability (in acetic acid, 1 M HCl, and water) as well as thermal
stability (up to 340 °C). Material 1′ was employed as a
heterogeneous solid catalyst for the ring opening of epoxides
by amines. Catalyst 1′ showed higher yields of the ring-opened
products and broad substrate scope for both epoxides and
amines. The catalyst displayed better activity than existing
Lewis acidic MOF catalysts such as Cu3(BTC)2, Fe(BTC), and
Zr-UiO-66. The exclusive role of 1′ in the catalytic reaction
was verified by executing control experiments with the free
linker and the zirconium salt and without catalyst 1′. The
reusability of the catalyst was illustrated up to five cycles. A
plausible mechanism for the catalytic reaction has been also
provided.
H
DOI: 10.1021/acs.inorgchem.9b02608
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Ketones: Application in the Synthesis of Convolutamydine A. Org.
Lett. 2007, 9, 5473−5476.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b02608.
■
S
́
́
(10) Andres, J. M.; Barrio, R.; Martínez, M. A.; Pedrosa, R.; Perez-
Encabo, A. Synthesis of Enantiopure syn-β-Amino Alcohols. A Simple
Case of Chelation-Controlled Additions of Diethylzinc to α-
(Dibenzylamino) Aldehydes. J. Org. Chem. 1996, 61, 4210−4213.
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aminoaldehydes via chelation-controlled additions. Total synthesis of
L-threo sphingosine and safingol. Tetrahedron Lett. 2012, 53, 4216−
4220.
Mass, NMR, EDX, and FT-IR spectra, simulated
structure, TG curves, pore size distribution plot,
PXRD patterns, nitrogen sorption isotherms, indexing
results, and FE-SEM images (PDF)
(12) Bergmeier, S. C. The Synthesis of Vicinal Amino Alcohols.
Tetrahedron 2000, 56, 2561−2576.
AUTHOR INFORMATION
Corresponding Authors
*A.D.: e-mail, admguru@gmail.com.
*S.B.: e-mail, sbiswas@iitg.ernet.in; tel, (+)91-3612583309;
fax, (+)91-3612582349.
■
(13) Tanaka, K.; Kinoshita, M.; Kayahara, J.; Uebayashi, Y.; Nakaji,
K.; Morawiak, M.; Urbanczyk-Lipkowska, Z. Asymmetric ring-
opening reaction ofmesoepoxides with aromatic amines using
homochiral metal−organic frameworks as recyclable heterogeneous
catalysts. RSC Adv. 2018, 8, 28139−28146.
ORCID
(14) Chen, W.; Zhou, Z.-H.; Chen, H.-B. Efficient synthesis of chiral
benzofuryl β-amino alcohols via a catalytic asymmetric Henry
reaction. Org. Biomol. Chem. 2017, 15, 1530−1536.
Helge Reinsch: 0000-0001-5288-1135
Amarajothi Dhakshinamoorthy: 0000-0003-0991-6608
Shyam Biswas: 0000-0001-7103-9939
(15) Kinage, A. K.; Upare, P. P.; Shivarkar, A. B.; Gupte, S. P. Highly
Regio-Selective Synthesis of β-Amino Alcohol by Reaction with
Aniline and Propylene Carbonate in Self Solvent System over Large
Pore Zeolite Catalyst. Green Sustainable Chem. 2011, 01, 76−84.
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
́
(16) Metro, T.-X.; Appenzeller, J.; Pardo, D. G.; Cossy, J. Highly
Enantioselective Synthesis of β-Amino Alcohols. Org. Lett. 2006, 8,
3509−3512.
Notes
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ring opening of epoxides with amines catalyzed by cyanuric chloride
under mild and solvent-free conditions. Green Chem. Lett. Rev. 2010,
3, 275−281.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
S.B. and A.D. are grateful for financial assistance from Science
and Engineering Research Board (SERB) through grant nos.
EEQ/2016/000012 and EMR/2016/006500, respectively.
A.D. is grateful to the University Grants Commission for an
Assistant Professorship award.
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Synthesis of β-amino Alcohols by Ring Opening of Epoxides. Res.
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DOI: 10.1021/acs.inorgchem.9b02608
Inorg. Chem. XXXX, XXX, XXX−XXX