Terbium–organic framework as heterogeneous Lewis acid catalyst for β-aminoalcohol synthesis: Efficient, reusable and green catalytic method

Article abstract of DOI:10.1002/aoc.3866

A terbium–organic framework (Tb-MOF) was prepared using a previously reported procedure. Tb-MOF was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, powder X-ray diffraction and surface area analysis. Tb-MOF was e

Full text of DOI:10.1002/aoc.3866

Received: 8 November 2016
DOI: 10.1002/aoc.3866
Revised: 22 March 2017
Accepted: 25 March 2017
F U L L PA P E R
Terbium–organic framework as heterogeneous Lewis acid catalyst
for β‐aminoalcohol synthesis: Efficient, reusable and green
catalytic method
Meghdad Karimi1
| Taraneh Hajiashrafi2
| Akbar Heydari1 | Alireza Azhdari Tehrani1
1 Chemistry Department, Tarbiat Modares
University, PO Box 14155‐4838, Tehran,
Iran
2 Department of Chemistry, Faculty of
Physics and Chemistry, Alzahra University,
PO Box 1993891176, Tehran, Iran
A terbium–organic framework (Tb‐MOF) was prepared using a previously reported
procedure. Tb‐MOF was characterized using Fourier transform infrared
spectroscopy, scanning electron microscopy, powder X‐ray diffraction and surface
area analysis. Tb‐MOF was employed as a heterogeneous Lewis acid catalyst for
the synthesis of β‐aminoalcohols. Also, the effect of ultrasonic irradiation was
examined in the catalytic aminolysis of styrene oxide. The reaction conditions were
optimized by variation of reaction time, catalyst concentration and solvent. A variety
of β‐aminoalcohols were synthesized and characterized. The Tb‐MOF catalyst
showed excellent selectivity and high yield for these transformations.
Correspondence
Taraneh Hajiashrafi, Department of
Chemistry, Faculty of Physics and
Chemistry, Alzahra University, PO Box
1993891176, Tehran, Iran.
Email: t.hajiashrafi@alzahra.ac.ir
KEYWORDS
Funding information
heterogeneous catalysis, metal–organic framework
Alzahra University; Tarbiat Modares
University; Iran National Science Foundation
(INSF)
1 | INTRODUCTION
particularly potent candidates for catalysis are MOFs with
coordinatively unsaturated metal sites where substrate
Metal–organic frameworks (MOFs) are a class of highly
tunable hybrid materials composed of metal ions that are
linked by organic bridges. The flexibility with which these
components can be varied has led to an extensive class of
MOF structures with potential applications in many areas,
including gas storage, molecular sensing and catalysis.[1]
Currently, the use of MOFs as catalysts is attracting
increasing attention as one of the hot topics in catalysis
research owing to their design versatility, porous structure,
high surface area and easy pre‐ and post‐modification.[2]
Several strategies have been presented in the literature for
the introduction of catalytically active sites to MOFs.[3]
According to the catalytically active sites, these frameworks
may be categorized into four distinct groups, namely MOFs
with coordinatively unsaturated metal sites (group I), MOFs
with metalloligands (group II), MOFs with catalytically
active centres at the organic linkers (group III) and MOFs
as support materials, which are used for immobilization of
an active component in the form of nanoparticles or clusters
inside the pores of the material (group IV).[4] Among these,
activation in catalytic reactions takes place at coordinatively
unsaturated framework metals. Such active sites are, in
general, occupied by solvent molecules that can be removed
by an activation process before catalytic reaction. In this case,
MOFs can act as heterogeneous Lewis acid catalysts because
of the Lewis acidity of the metal centres which can activate
organic molecules via metal–organic interactions in catalysis.
Cu‐HKUST‐1, Cr‐MIL‐101 and Mg‐MOF‐74 represent the
most well‐known examples of MOFs with open metal sites,
which have demonstrated a potential for catalytic activities.[5]
Recently, lanthanide MOFs (Ln‐MOFs) have received
considerable attention due to their intriguing topological
structures and exceptional optical and magnetic properties.[4]
Although Ln‐MOFs are expected to be potential
heterogeneous Lewis acid catalysts, only a few reactions
including epoxidation of olefins, oxidation of organic sulfurs
and acetalization of aldehydes catalysed by Ln‐MOFs have
been reported.[6] In this regard, we are interested in exploring
the potential of Ln‐MOFs as catalysts for organic
transformations.
Appl Organometal Chem. 2017;e3866.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.3866

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KARIMI ET AL.
Recently Xu and co‐workers reported a series of
isostructural Ln‐MOFs (Ln = Tb, Dy, Er, Yb) of the general
formula Ln(BTC)(H2O)3(DMF)1.1 (BTC 1,3,5‐
biologically active natural and synthetic products, non‐natural
amino acids and chiral auxiliaries.[8] Therefore, there is a sig-
nificant interest in the development of environmentally
friendly and sustainable methods for the ring opening of
epoxides. In most cases, the synthetic methods involve
heating an epoxide in a protic solvent with excess amine.
The non‐catalytic aminolysis procedure is satisfactory in
many cases. However, it suffers from many disadvantages,
including the use of high temperatures or prolonged reaction
times.[9] Several modifications of the classical procedures
have been reported to overcome these limitations and a
variety of catalytic systems such as LiClO4, Zn(OTf)2,[10]
LiBF4, CaCl2,[11] LiOTf,[12] CoCl2,[13] Ln(OTf)3 (Ln = Yb,
Nd, Gd),[14] ZrCl4,[15] VCl3,[16] SmCl3,[17] Cu(OTf)2,[18]
Sn(OTf)2,[19] [(CH3)2CHO]2AlOOCCF3,[20] CeCl3⋅7H2O–
NaI,[21] Bi(OTf)3 and Bi(TFA)3 under microwave irradia-
tion,[22] alumina,[23] silica under high pressure,[24]
montmorillonite clay under microwave irradiation,[25] tita-
nia–iron(III) oxide[26] and Fe(III)–salen grafted SBA‐15[27]
have been used in this regard. Although significant advances
have been made in this area within the past few years, low
regioselectivity, longer reaction time, use of elevated
temperature, high catalyst loading, toxic solvents and lower
substrate compatibility limit their applications. Thus there is
a need to develop an efficient catalytic protocol for ring
opening of various epoxides with aliphatic and aromatic
amines under ambient conditions.
=
benzenetricarboxylate; DMF = N,N‐dimethylformamide),
which showed high thermal and chemical stability.[6] These
compounds were solvothermally obtained and their structures
determined using X‐ray crystallography. According to the
reported procedure, reaction between terbium(III) nitrate
hexahydrate and BTC in mixed solvents of DMF and water
inside a Teflon‐lined autoclave at 105°C for 24 h yielded
Tb(BTC)(H2O)3(DMF)1.1, which was characterized using
powder X‐ray diffraction (PXRD), Fourier transform infrared
(FT‐IR) spectroscopy and surface area analysis. The Tb(III)
coordination environment can be considered as a distorted
pentagonal bipyramidal geometry formed by six oxygen
atoms from six carboxylate groups of six BTC ligands and
one oxygen atom from the terminal water molecule. The open
terbium sites are generated during the activation process
(330°C for 4 h) as result of the removal of coordinated water
and DMF molecules, trapped in pores, that remain after the
MOF synthesis. The high thermal stability, accessible open
metal sites and nano‐sized aperture for the Tb‐MOF could
endow it with a very high potential in catalysis.
Epoxides are some of the most important synthetic
intermediates in organic synthesis and a variety of reagents
are known to nucleophilically open the epoxide ring.[7] β‐
Aminoalcohols are versatile synthons for a wide range of
TABLE 1 Optimization of reaction of epoxy and amine, at room temperature and under ultrasonic condition
Entry
Catalyst (mg)
Condition
Time (min)
Temperature (°C)
Yield (%)
1
20
20
20
20
20
20
20
10
40
60
20
20
20
20
20
20
20
20
Solvent free
H2O
30
30
30
30
30
30
30
30
30
30
60
60
60
60
60
60
60
90
RT
<5
50
60
ND
ND
ND
80
45
80
77
85
84
86
85
85
86
85
95
2
RT
3
MeOH
Toluene
n‐Hexane
Acetonitrile
EtOH
RT
4
RT
5
RT
6
RT
7
RT
8
EtOH
RT
9
EtOH
RT
10
11
12
13
14
15
16
17
18
EtOH
RT
RT
EtOH
EtOH
40
EtOH
60
EtOH
Reflux temperature
RT (ultrasonic irradiation)
40 (ultrasonic irradiation)
80 (ultrasonic orradiation)
RT (ultrasonic irradiation)
EtOH
EtOH
EtOH
EtOH

KARIMI ET AL.
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In order to understand the scope and limitations of this
catalytic methodology, various amines were treated with
styrene oxide under optimized conditions in the presence of
Tb‐MOF. The reaction was found to be fast and nearly com-
plete conversion was obtained within 15–30 min, leading to
2 | EXPERIMENTAL
2.1 | General
All materials were purchased from Merck and used without fur-
ther purification. The reactions were precisely monitored using
analytical TLC with ethyl acetate and n‐hexane as eluents. Due
to the need to achieve final pure and isolated target molecules, a
scaled‐up TLC was conducted with Merck 0.2 mm silica gel
60F‐254 Al‐plates. FT‐IR spectral analysis was performed with
a Shimadzu FT‐IR‐8400S spectrometer and definite character-
ization of all novel products was done with 1H NMR
(500 MHz) and 13C NMR (125 MHz) spectra recorded with
TABLE 2 Application of Tb‐MOF for synthesis of β‐aminoalcohols
under optimized reaction conditions
Entry
Oxirane
Amine
Yield (%)
1
95
a
Bruker DRX‐500 Avance spectrometer using
dimethylsulfoxide as solvent at ambient temperature (relative
to tetramethylsilane as internal standard). All yields referred
to the isolated products. Scanning electron microscopy
(SEM) images were obtained with a Zeiss‐Sigma VP 500. Pri-
mary results for progress of reactions were obtained using GC
on an ECHROM A 90 with toluene as general solvent for injec-
tion and nitrogen as inert carrier gas.
2
3
4
90
80
60
2.2 | Preparation of Tb‐MOF
TB‐MOF was synthesized according to
a reported
procedure.[6] A mixture of Tb(NO3)3⋅6H2O (0.5 mmol), ben-
zene‐1,3,5‐tricarboxylic acid (0.25 mmol), DMF (4 ml) and
water (4 ml) was sealed in a 20 ml Teflon‐lined reactor. Pure
colourless needle crystals of Tb(BTC)(H2O)(DMF)1.1 with a
yield of 45% were obtained after 24 h of heating at 105°C.
Anal. Calcd for Tb(BTC)(H2O)(DMF)1.1 (%): C, 31.25; H,
2.71; N, 3.26. Found (%): C, 31.22; H, 2.62; N, 3.30. FT‐IR
(cm−1): 1611 m, 1572 w, 1536 w, 1433 m, 1372 s, 1103 w,
939 w, 770 s, 714 m, 702 vs, 666 m, 563 s, 455 s, 434 m, 417
w. For the purpose of activation, according to the
thermogravimetric analysis pattern, whenTb‐MOF was heated
to 330°C for 4 h, the coordinating DMF molecules began to be
removed, and the compound retained its stability up to temper-
atures of 450°C. Anal. Calcd for Tb(BTC)(H2O)(DMF)1.1 (%):
C, 28.87; H, 0.81. Found (%): C, 28.78; H, 0.93. FT‐IR (cm−1):
1611 m, 1572 w, 1536 w, 1433 m, 1372 s, 1103 w, 939 w,
770 s, 714 m, 702 vs, 666 m, 563 s, 455 s, 434 m, 417 w.
5
6
75
75
7
8
9
80
65
70
10
11
12
65
65
85
2.3 | General procedure for preparation of β‐
Aminoalcohols
For optimization of the reaction conditions, a specified amount
of Tb‐MOF was added to a mixture of aniline and styrene oxide
in an ultrasonic water bath for different periods of time
(Table 1).[5,11] The progress of the reactionwas monitored using
TLC. After completion of the reaction, the catalyst was sepa-
rated by centrifuging and the products were purified by non‐
flash chromatography of the reaction mixture via silica plate.

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KARIMI ET AL.
FIGURE 3 Nitrogen adsorption and desorption isotherms for Tb‐
MOF at 77 K
4.05–3.95 (2H, m, OCH2), 3.67–3.52 (2H, m, OH, NH),
3.43–3.24 (2H, m, CH2N). 13C NMR (300 MHz, CDCl3, δ,
ppm): 161.2, 149.6, 131.0, 131.2, 122.1, 119.1, 117.3,
114.3, 71.8, 69.5, 48.6.
FIGURE 1 Representation of the pores of terbium metal–organic
framework
2.3.2 | 1‐(N‐4‐Methoxyphenyl)amino‐3‐
phenoxy‐2‐propanol (12)
the quantitative yield of the corresponding 2‐aminoalcohols
1
(Table 2). FT‐IR, H NMR and 13C NMR data for selected
FT‐IR (KBr, νmax, cm−1): 3413, 2924, 2859, 1596, 1496,
compounds are summarized below.
1
1450, 1395, 1242, 1182, 1098, 1040. H NMR (300 MHz,
CDCl3, δ, ppm): 7.38–7.26 (2H, m, Ph), 7.06–6.91 (3H, m,
Ph), 6.81 (2H, d, Ph), 6.71 (2H, d, Ph), 4.28 (1H, s,
CH─OH), 4.09–4.03 (2H, m, OCH2), 3.79 (3H, s, OCH3),
3.62 (2H, s, NH, OH), 3.43–3.35 (1H, m, CH2N),
3.27–3.23 (1H, m, CH2N). 13C NMR (300 MHz, CDCl3, δ,
ppm): 191.2, 151.5, 142.7, 131.4, 122.1, 116.8, 116.7,
116.2, 68.8, 67.4, 56.5, 48.7.
2.3.1 | 1‐(N‐Phenyl)amino‐3‐phenoxy‐2‐
propanol (11)
FT‐IR (KBr (liquid film), νmax, cm−1): 3395, 2924, 2858,
1
1595, 1496, 1397, 1242, 1098, 1040. H NMR (300 MHz,
CDCl3, δ, ppm): 7.37–7.13 (4H, m, Ph), 7.07–6.86 (3H, m,
Ph), 6.81–6.67 (3H, m, Ph), 4.32–4.21 (1H, m, CH─OH),
FIGURE 2 PXRD patterns of Tb‐MOF: simulated, as‐synthesized, after catalytic reaction and after recycling (10 times)

KARIMI ET AL.
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3 | RESULTS AND DISCUSSION
3.1 | Characterization of Tb‐MOF
SCHEME 1 Synthesis of β‐aminoalcohols catalysed by Tb‐MOF
Tb‐MOF was synthesized and then characterized using
various techniques (Figure 1). FT‐IR spectroscopy, elemen-
tal analysis and PXRD confirmed the formation of
Tb(BTC)(H2O)(DMF)1.1 (Figure 2). The MOF was acti-
vated at 330°C under vacuum for 4 h to remove any resid-
ual and coordinated solvent molecules. The activation of
this framework was confirmed from FT‐IR spectra, ele-
mental analysis and PXRD analysis (Figure 2). Also, the
BET surface area of the activated Tb‐MOF was determined
as 582 m2 g−1 (Figure 3). which is comparable to the
reported surface area.[8] The morphology of Tb‐MOF pre-
pared by the solvothermal method was characterized using
field emission FE‐SEM before and after catalytic reaction.
As illustrated in Figure 4, the retention of morphology
during the transformation suggests considerable stability,
which is necessary for performing a reaction in the pres-
ence of a heterogeneous catalyst. The high thermal stabil-
ity, accessible open metal sites and nano‐sized aperture
of Tb‐MOF could endow it with a very high potential in
catalysis.
stirred at room temperature under ultrasonic irradiation and
monitored by TLC.
After completion of the reaction, the catalyst was easily
separated by centrifugation. To find the optimal reaction
conditions, various conditions were investigated. The
reaction was optimized by variation of the reaction time, tem-
perature, reaction solvent and catalyst concentration
(Table 1). Also, the PXRD pattern of Tb‐MOF after the
catalytic reaction indicates that the framework remains intact
(Figure 2). as supported by the good agreement between the
FT‐IR measurements before and after the reaction. Various
solvents were investigated for this reaction. Ethanol improved
the yield of the conversion compared to CH3OH, CH3CN,
H2O and CHCl3. Notably, the yield of the transformation
increases when the reaction temperature is increased to 90
from 30°C and when the time is increased (Table 1, entries
7, 12, 13 and 14).The reaction proceeded rapidly, and it
was completed after 90 min at room temperature (Table 1,
entry 18). The reaction was carried out in the presence of
10, 20, 40 and 60 mg of Tb‐MOF, resulting in the isolation
of the product in yields of 45, 80, 80 and 77%, respectively.
It should be pointed out that, in the absence of catalyst, the
reaction was very slow, and even after a prolonged reaction
time considerable amounts of starting materials remained
unreacted (yield <10%). After finding the optimized reaction
conditions we continued our investigation by reacting a series
3.2 | Application of Tb‐MOF for synthesis of
β‐Aminoalcohols
Tb‐MOF was investigated as a heterogeneous Lewis acid
catalyst for the synthesis of β‐aminoalcohols. To a mixture
of epoxide (1 mmol) and amine (1 mmol) in water (3 ml),
Tb‐MOF was added (Scheme 1). The reaction mixture was
FIGURE 4 SEM analysis of Tb‐MOF particles (a) before and (b) after reaction

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KARIMI ET AL.
of amines with styrene oxide (Table 2).[5,6,8,11] Various
amines were used as substrates in the reaction. The observed
catalytic changes have been correlated to steric and electronic
factors. Amines with electron‐withdrawing groups and with
steric hindrance were less reactive, whereas amines with
electron‐donating groups promote the transformation in high
yield (Table 2). The in situ FT‐IR spectrum after adsorption
of pyridine shows three bands at 1018, 1110 and 1226 cm−1
(Figure 5), which are assigned to the pyridine chemisorbed
on Tb3+ Lewis acid sites of Tb‐MOF.[28] Considering that
the molar absorption coefficient of Tb‐MOF at around
1110 cm−1 is 1.58 cm μmol−1 determined by adsorption of
calibrated doses of pyridine, the concentration of the Lewis
acid sites in the currently synthesized Tb‐MOF can be
quantified as about 38% of the total number of Tb atoms
contained in this framework.
3.3 | Catalyst reusability
From an industrial point of view, the reusability of a cata-
lyst is important for large‐scale operation. Therefore, the
reusability of the catalyst was examined in the reaction of
styrene oxide and amine. The catalyst can be separated from
the reaction medium by centrifuging; therefore it could be
recovered simply by centrifugation followed by washing
with ethanol and drying at 50°C. Afterwards, the catalyst
can be weighed and used directly in the next cycle of the
reaction using fresh substrates. The results showed that the
catalyst could be reused ten times without appreciable loss
of activity (Figure 6). Further investigation of the heteroge-
neous character of the catalytic system as well as of the sta-
bility of the structure was carried out using a hot filtration
test. After 2 h of sonication, the reaction mixture was cen-
trifuged and the catalyst was filtered off. Then, the superna-
tant was sonicated at room temperature. Interestingly, within
4 h of further reaction time, no distinguishable changes
were recognized in the reaction conversion. Also, the
PXRD pattern of Tb‐MOF indicates that the framework
remains intact after the catalytic reaction, as supported by
the good agreement between the FT‐IR measurements
before and after the reaction. In comparison with other
reported catalytic systems for the aminolysis of epoxides,
Tb‐MOF showed good catalytic performance in terms of
activity and reusability (Table 3).
FIGURE 5 FT‐IR spectrum of activated Tb‐MOF after adsorption of
pyridine and followed by evacuation at room temperature
FIGURE 6 Loss of activity as a function of the number of recycles of
Tb‐MOF for the synthesis of β‐aminoalcohol
TABLE 3 Performance of some reported catalytic systems for aminolysis of epoxides
Yield (%)
Ref.
Amount (mg)
Temperature (°C)
Time (min)
Solvent
Catalyst
[29]
[30]
[23]
[31]
[8]
92
82
69
88a
98
96
88
95
20
10
RT
45
180
360
480
300
0.33
180
30
—
nano Fe(OH)3
Fe3O4@SiO2‐SO3H
Al2O3
RT
EtOH
THF
6000
Reflux
60
H2O
β‐Cyclodextrin
LiBr
5 mol%
RT
—
[22]
[7]
0.05 mol%
Microwave oven
CH3CN
Cyclohexane
EtOH
Bi(OTf)3
RT
RT
Polymer/CuSO4
Tb‐MOF
This work
20
aReaction between thioacids and epoxides.

KARIMI ET AL.
7 of 7
[9] I. Cepanec, M. Litvić, H. Mikuldaš, A. Bartolinčić, V. Vinković,
Tetrahedron 2003, 59, 2435.
4 | CONCLUSIONS
[10] M. Chini, P. Crotti, F. Macchia, J. Org. Chem. 1991, 56, 5942.
[11] M. Chini, P. Crotti, F. Macchia, Tetrahedron Lett. 1990, 31, 4661.
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MOFs can act as heterogeneous catalysts for a variety of
organic reactions, especially for liquid‐phase reactions. The
catalytic applications of MOFs are often limited by their
chemical, hydrolytic and thermal stabilities. MOFs based on
lanthanides are a very promising class of materials for
addressing the challenges of heterogeneous Lewis acid catal-
ysis. In summary, herein, Tb‐MOF as a heterogeneous Lewis
acid catalyst and ultrasonic irradiation as synergic factor were
used for epoxy aminolysis reaction at room temperature. The
framework has open metal sites at Tb(III) centres, thus pro-
viding accessible Lewis acid centres for electrophile activa-
tion. We have presented a new catalytic system which
proves to be very effective not only in reducing the reaction
time, but also in increasing the yield of the product. It
involves a simple procedure, is environmentally friendly
and also incorporates special features like reagent economy,
easy workup and easy handling.
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ACKNOWLEDGEMENTS
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33, 304.
We gratefully acknowledge financial support from the
Research Council of Alzahra University, Tarbiat Modares Uni-
versity and from the Iran National Science Foundation (INSF).
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