Cu-MOF-Catalyzed Carboxylation of Alkynes and Epoxides

Article abstract of DOI:10.1134/S1070428019120017

The catalytic activity of copper-containing heterogeneous catalysts, in particular metal-organic frameworks, zeolites, and alumina-supported nanoparticles, in the carboxylation of terminal alkynes and oxiranes has been evaluated. Temperature dependences of these reactions have been studied.

Full text of DOI:10.1134/S1070428019120017

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 12, pp. 1813–1820. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 12, pp. 1813–1821.
Cu-MOF-Catalyzed Carboxylation of Alkynes and Epoxides
a
a
b
a, b
a
O. G. Ganina ,* G. N. Bondarenko , V. I. Isaeva , L. M. Kustov , and I. P. Beletskaya **
a
Faculty of Chemistry, Moscow State University, Moscow, 119991 Russia
b
Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991, Russia
e-mail: *gognn@rambler.ru; **beletska@org.chem.msu.ru
Received July 19, 2019; revised October 24, 2019; accepted October 24, 2019
Abstract—The catalytic activity of copper-containing heterogeneous catalysts, in particular metal–organic
frameworks, zeolites, and alumina-supported nanoparticles, in the carboxylation of terminal alkynes and
oxiranes has been evaluated. Temperature dependences of these reactions have been studied.
Keywords: metal–organic frameworks, catalysis, copper, carboxylation, alkynes, epoxides.
DOI: 10.1134/S1070428019120017
Carbon dioxide is one of the greenhouse gases, and
its utilization is an important environmental problem.
On the other hand, nontoxic carbon dioxide is very
promising for organic synthesis since it can be regard-
ed as a convenient and safe substitute for isocyanates
and phosgene. Carbon dioxide can be chemically
captured via reactions with alkenes, alkynes, dienes,
enynes, and aromatic or heteroaromatic compounds
catalytic properties by variation of the metal nature,
functionality and size of the linker, position of func-
tional groups, and/or pore size and shape, which allows
the selectivity of catalysis to be controlled [15–17]. In
addition, MOFs are efficiently used for adsorption and
storage of gases, including carbon dioxide, as well as
for separation of gas mixtures [18]. This makes them
promising as carboxylation catalysts.
[
1–3]. Among the reactions of carbon dioxide leading
There are published data on the synthesis of cyclic
carbonates and polycarbonates by cycloaddition of
carbon dioxide to oxiranes in the presence of MOFs
based on zinc [19, 20], cobalt [21], zirconium [22],
manganese [23], chromium [24], iron [24], indium
to the formation of useful organic compounds, of
exceptional importance is carboxylation of epoxides to
produce cyclic carbonates [4] that are used as elec-
trolytes in lithium ion batteries, aprotic polar solvents,
and synthetic intermediates [5–7]. Another important
reaction is carboxylation of acetylenes, which leads to
the formation of propiolic acid derivatives [8–11]
widely used in organic synthesis.
[22], and hafnium [25]. A few examples of carboxyla-
tion catalyzed by copper-based MOFs have also been
reported. In particular, copper MOF obtained from
aminoterphenyltetracarboxylic acid efficiently cata-
lyzed cycloaddition of carbon dioxide to epoxides
It should be noted that carbon dioxide molecule is
characterized by high kinetic and thermodynamic sta-
bilities; therefore, carboxylation reactions require the
use of either active substrates such as organometallic
compounds [12] or active catalysts [13]. The catalyst
should be efficient, available, stable, and recyclable.
These properties are intrinsic to heterogeneous cata-
lysts based on transition metals, such as metal–organic
frameworks, metal-containing zeolite structures, and
metal nanoparticles immobilized on various polymeric
or inorganic supports.
under mild conditions (room temperature, CO pres-
2
sure 1 atm) [26]. A MOF based on copper 2,5-ditri-
azolylterephthalate provided a higher substrate conver-
sion than did copper benzene-1,3,5-tricarboxylate
HKUST-1 (86 and 67%, respectively). However, in the
latter case, an Ν /CO gas mixture was used, so that
2
2
the lower yield of cyclic carbonates could be caused
by the lower concentration of CO in the reactor [27].
2
Catalysts for the carboxylation of propylene oxide and
epichlorohydrin were obtained by encapsulation of
copper, aluminum, cobalt, and nickel phthalocyanines
in faujasite type zeolite (zeolite-Y) [28].
Metal–organic frameworks (MOFs) are a new class
of highly porous hybrid materials that are cage struc-
tures formed by metal ions and organic bridging
ligands (linkers) [14]. Metal–organic frameworks are
advantageous due to the possibility of changing their
We previously studied carboxylation of epoxides
catalyzed by zinc chloride immobilized on various
inorganic supports in the presence of tetrabutylammo-
1
813

1
814
GANINA et al.
(a)
(b)
Fig. 1. (a) Copper-containing heterogeneous catalysts HKUST-1 (1), CuCa-LSF (2), and Cu/Al O (3); (b) SEM image of catalyst 3.
2
3
nium halide (Bu NX) as a nucleophilic additive.
were 78 and 83%, and at 50°C, 47 and 53%, respec-
tively. The reactions at room temperature were very
slow, and the yield of 5a did not exceed 20% after 15 h
and 30% after 48 h. It should be noted that in the
reaction catalyzed by Cu/Al O , raising the tempera-
4
Among the catalysts used, ZnCl /Al O turned out to
2
2
3
be the most efficient and selective [29]. We also
studied carboxylation of alkynes catalyzed by oxide-
supported copper nanoparticles, where Cu/Al O
2
3
2
3
showed the highest activity [30]. These findings, as
well as published data on the use of Cu-MOFs and
zeolites as catalysts [27, 28], prompted us to compare
the catalytic activities of copper benzene-1,3,5-tricar-
boxylate (HKUST-1, 1) [27] and copper-containing
bimetallic zeolite based on low-silicon faujasite
ture to 80–100°C dramatically reduced the yield (by
15–20%), which may be due to lower solubility of
carbon dioxide at elevated temperature. In contrast,
catalysts 1 and 2 that effectively adsorb and retain CO2
provided higher yields as the temperature rose.
Thus, a high yield of 5a can be achieved at 80°C
(CuCa-LSF, 2) [31] with the activity of alumina-sup-
(76 and 83% in 15 h or 86 and 92% in 20 h for
ported copper nanoparticles (40–70 nm; Cu/Al O , 3)
2
3
catalysts 1 and 2, respectively). The yield significantly
decreased when a lower amount of Cu-MOF was used
(Fig. 1) [30] in the above reactions. The morphology
and particle size of these catalysts were studied pre-
viously [30–32], but no comparative analysis of their
catalytic activity was performed.
(61% for 1 mol % of 1 and 33% for 0.2 mol % of 1).
Rise in the carbon dioxide pressure had a positive
but insignificant effect on the yield of 5a which
increased by 4–7% for every 2-atm increment in the
CO pressure. Therefore, a CO pressure of 2 atm was
The carboxylation of styrene oxide 4a with CO2
(
2 atm) in the presence of 1.5 mol % of tetrabutyl-
2
2
ammonium bromide (TBAB) was used as a model
reaction. The reactions were carried out under solvent-
free conditions at various temperatures (Scheme 1,
Fig. 2). In the presence of Cu-MOF 1 and copper
zeolite 2, the complete conversion of 4a was achieved
in 15 h at 100°C, whereas the conversions at 80°C
assumed to be optimal.
Variation of the nucleophilic additive showed that
tetrabutylammonium iodide (TBAI) provided the best
results. However, the difference in the yields between
TBAI and TBAB was insignificant, so that more
available TBAB was used in further experiments. No
reaction occurred in the absence of a nucleophilic ad-
ditive. As a rule, the reaction requires no solvent, since
both initial oxirane and the resulting cyclic carbonate
act as a reaction medium.
Scheme 1.
O
1, 3 (2 mol %) or 2 (3 mg)
4
Bu NBr (1.5 mol %), Δ, 15 h
O
+
CO
2
O
O
Temperature, °C
Ph
Ph
Fig. 2. Temperature effect on the carboxylation of 2-phenyl-
oxirane (4a) in the presence of catalysts 1–3.
4
a
2 atm
5a
0.2 mmol
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019

Cu-MOF-CATALYZED CARBOXYLATION OF ALKYNES AND EPOXIDES
1815
Scheme 2.
O
1, 3 (2 mol %) or 2 (3 mg)
80°C, 20 h
O
R
0
+ CO
2
O
O
R
R'
R'
5a–5g
4
a–4g
.2 mmol
2 atm
Yield of 5, %
Catalyst 1 Catalyst 2 Catalyst 3
Compound no. R, R'
5
5
5
5
5
a
b
c
d
e
Ph, H
4-ClC
86
77
92
89
51
–
6 4
H , H
Me, H
ClCH
100
98
100
96
82
–
2
, H
CH =CHCH CH , H
2
2
2
93
98
73
59
17
5
f
PhOCH
2
, H
85
97
5g
Me, Me
52
49
Under the optimized conditions, we examined car-
boxylation of a series of alkyl- and aryloxiranes 4a–4g
in the presence of copper-containing catalysts 1–3
yield (1) or with an insignificantly reduced yield (2).
In contrast, the catalytic activity of 3 considerably de-
creased even in the second cycle (Fig. 3). Thus, though
the Cu-MOF catalyst was somewhat inferior to zeolite-
based one in terms of yield, it was superior in terms of
reusability.
(Scheme 2). Catalysts 1 and 2 provided high to excel-
lent yields of 5a–5f (77–100%) from monosubstituted
oxiranes 4a–4f, whereas in the reactions catalyzed by
Cu/Al O (3) the yields of alkyl derivatives were
somewhat higher (5c, 82%; 5e, 73%) than the yield of
phenyldioxolane 5a (51%). 2,2-Dimethyloxirane (4g)
2
3
Published data on the carboxylation of styrene
oxide over heterogeneous copper catalysts [22, 24, 26–
2
8, 32] are given in Table 1. Under the conditions
reacted with CO more poorly in the presence of all
2
proposed by us, the catalytic activities of HKUST-1
and CuCa-LSF were comparable to or exceeded the
activity of other copper-based MOFs.
tested catalysts (yield of 5g 52, 49%, and 17% for
catalysts 1–3, respectively); however, the half-conver-
sion was achieved during the same period using porous
catalysts 1 and 2 (HKUST-1 and CuCa-LSF).
Catalysts 1–3 were also evaluated in the carboxyla-
tion of terminal alkynes. This reaction is usually
carried out in the presence of copper(I) [33–36] or
silver salts and complexes [37–39]. However, in the
past decade extensive studies were aimed at searching
for heterogeneous catalytic systems for carboxylation
We also found that in the reactions catalyzed by
CuCa-LSF and HKUST-1 the addition of a new portion
of substrate 4a after the reaction was complete (fresh
start) gives rise to a new cycle either without loss of
Table 1. Carboxylation of 2-phenyloxirane (4a) in the presence of copper-containing heterogeneous catalysts
Catalyst Amount, mol % Temperature, °C Reaction time, h P(CO ), atm Yield of 5a, % Reference
HKUST-1
2
0.32
1.1
0.2
0.2
0.48
0.48
0.4
2.8
2
80
25
25
25
80
16
48
8
24
24
24
4
1
8
1
Air
0.85 (+N2)
0.85 (+N2)
6.8
7
2
42
10
89
45
67
86
65
34
86
94
51
[22]
[24]
[26]
[26]
[27]
[27]
[28]
[32]
HKUST-1
Cu(II)-MOF
Cu(II)-MOF
HKUST-1
FJI-H14
CuPc-Y-zeolyte
HKUST-1
HKUST-1
LSF
80
120
100
80
80
80
4
15
15
15
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This work
This work
2
2
2
2
Cu/Al O
2
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019

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816
GANINA et al.
added to simplify the isolation procedure and analysis
of the product which was formed as butyl ester, as well
as to shift the carboxylation–decarboxylation equilib-
rium toward product formation. The catalytic activities
of 1–3 were compared in the carboxylation of 4-me-
thoxyphenylacetylene 6a (Scheme 3, Fig. 4). The yield
1
of ester 7a was determined by H NMR.
The complete conversion of 6a under catalysis by
HKUST-1 was achieved at 70–80°C in 16 h. The yield
of 7a was also high (97%) at 60°C, whereas it
decreased to 61% at 40°C. In the reaction catalyzed by
CuCa-LSF, the yield linearly increased with tempera-
ture, but the conversion was not complete even at 80°C
Cycle no.
Fig. 3. Fresh-start carboxylation of 2-phenyloxirane (4a) in
the presence of catalysts 1–3.
(yield 83%). The conversion of 6a was almost com-
plete in the presence of Cu/Al O at 60°C, but the yield
2
3
of 7a abruptly decreased as the temperature rose
66% at 70°C and 32% at 80°C). A similar pattern was
(
observed for carbon-supported catalyst [40] and was
explained by increase of the rate of decarboxylation at
elevated temperature [30]. However, highly porous
catalysts such as 1 and 2 are free from this drawback
due to efficient adsorption of CO , which provides
2
easy access to carbon dioxide by the substrate and shift
of the equilibrium toward product formation. In all
cases, the reaction at room temperature was slow, and
the yield of 7a did not exceed 20%. Thus, the optimal
reaction temperature for porous catalysts 1 and 2 is
Temperature, °C.
Fig. 4. Temperature effect on the carboxylation of 4-me-
thoxyphenylacetylene (6a) in the presence of catalysts 1–3.
8
0°C, whereas Cu/Al O (3) is more efficient at 60°C,
2 3
and the activity of the latter exceeds that of the homo-
geneous CuI–phenanthroline system (yield 97 and
of alkynes. In particular, NHC (N-heterocyclic car-
bene) polymeric systems based on copper(I) chloride
7
6%, respectively).
(CuCl-polyNHC) [35] and silver nanoparticles [9],
activated carbon-supported copper bromide [40], and
silver-containing MOFs based on chromium (MIL-
A series of terminal alkynes 6a–6e were subjected
to carboxylation under the optimal conditions (2 equiv
of Cs CO , 5 mol % of catalyst 1–3, 1.5 equiv of BuBr,
1
01) [41], cobalt [42], and zirconium (core–shell nano-
2
3
CO pressure 2 atm, solvent DMF, temperature 80 or
structures; UiO-66@UiO-67-BPY-Ag) [43] have been
proposed. As we already noted, Al O -supported cop-
2
6
0°C; Scheme 4). Unsubstituted phenylacetylene (6b)
2
3
and its analogs 6a and 6c with electron-donating
substituents in the benzene ring were converted to the
corresponding butyl propiolates 7a–7c in nearly quan-
titative yields in the presence of HKUST-1 (7a–7c,
100%) and Cu/Al O (7a, 7c, 97%; 7b, 100%; 60°C)
per catalyst also efficiently catalyzed this reaction [30].
In this work, the carboxylation of terminal alkynes
was carried out using 5 mol % of catalyst 1–3, di-
methylformamide as a solvent, and cesium carbonate
2
3
(2 equiv) as a base. Butyl bromide (1.5 equiv) was also
and in high yields in the presence of CuCa-LSF (7a,
Scheme 3.
O
1
, 3 (5 mol %) or 2 (5.6 mg)
CH
Cs CO (2 equiv), BuBr (1,5 equiv)
OBu
2
3
DMF, 80°C, 16 h
+
CO2
MeO
MeO
6
a
2 atm
7a
0
.15 mmol
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019

Cu-MOF-CATALYZED CARBOXYLATION OF ALKYNES AND EPOXIDES
1817
Scheme 4.
O
1
, 3 (5 mol %) or 2 (5.6 mg)
Cs CO (2 equiv), BuBr (1,5 equiv)
DMF, 80°C, 16 h
2
3
CH
OBu
+
CO
2
R
R
6a–6e
2 atm
7a–7e
0.15 mmol
Yield of 7, %
Catalyst 1 Catalyst 2 Catalyst 3, 60°C
Compound no.
R
7
a
4-MeOC H4
100
100
100
82
83
88
79
64
58
97
100
97
6
7b
Ph
7c
4-t-BuC
4-FC
6 4
H
7d
6
H
4
67
7e
C
5
H
11
71
52
8
3%; 7b, 88%; 7c, 79%). The yields of 7d containing
of a larger contribution of the decarboxylation process.
The amount of the catalyst in the reaction with alkynes
an electron-withdrawing fluorine atom in the benzene
ring and 7e (aliphatic alkyne) were lower (82, 64, and
was higher than in the cycloaddition of CO to oxiranes
2
6
7% and 71, 58, and 52% for catalysts 1–3, respec-
(5 and 2 mol %, respectively). The effects of substit-
uents in the substrates were also different for oxiranes
and alkynes. Monoalkyl-substituted oxiranes reacted
slightly more readily than their aryl-substituted analog
and significantly better than 2,2-disubstituted oxirane.
Contrastingly, aliphatic alkynes were considerably less
reactive than arylacetylenes, especially those with elec-
tron-donating substituents. Furthermore, zeolite cata-
lyst 2 was much less efficient than Cu-MOF in the
carboxylation of alkynes, whereas their efficiencies
in the carboxylation of epoxides were fairly similar.
A probable reason is that copper(II) predominates in
CuCa-LSF, whereas HKUST-1 and Cu/Al O contain
tively). We succeeded in performing several further
cycles of carboxylation of 6a at 60°C (fresh-start)
without significant loss of catalytic activity (Fig. 5);
the best results were obtained using Cu-MOF 1.
Published data on the carboxylation of phenylacety-
lene [9, 35, 41] are presented in Table 2. It is seen that
under the given conditions, the catalytic activities of
HKUST-1 and Cu/Al O are comparable to or exceed
those found for other copper- and silver-based hetero-
geneous catalytic systems.
2
3
As follows from Figs. 2 and 4, both carboxylation
reactions showed similar temperature dependences for
copper catalysts. The activity of porous catalysts 1 and
2
3
large amounts of copper(I) [30, 44] which catalyzes the
carboxylation process.
2
increased with temperature. In contrast, the catalytic
efficiency of alumina-supported copper nanoparticles
catalyst 3) decreased as the temperature rose above
0–75°C due to weaker adsorption of CO at elevated
In summary, copper-containing heterogeneous
catalysts are efficient in the carboxylation of alkynes
and epoxides. The copper-containing catalyst based
on a porous metal–organic coordination polymer per-
sistently showed a high activity in both reactions,
(
6
2
temperature. The catalytic activity of 3 in the carbox-
ylation of alkynes dropped to a greater extent because
Table 2. Carboxylation of phenylacetylene (6b) in the presence of copper- and silver-containing heterogeneous catalysts
Temperature,
Reaction
time, h
Yield of 7b,
Metal
Catalyst, mol %
P(CO ), atm
Reference
2
°
C
%
Cu
Cu
Ag
Ag
Cu
Cu
Cu
P(NHC) (NHC-Cu)
1
1
1
1
2
2
2
25
25
16–24
24
95
90
[35]
[35]
0
.5
0.5
0.5
P(NHC) (NHC-Cu)
0
.5
AgNPs MIL-101 zeolite-type MOF, 2.7
50
15
99
[41]
Poly-NHC
HKUST-1, 5
CuCa-LSF
Cu/Al O , 5
25
98
[9]
60/80
80
16
16
16
97/100
88
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60/80
97/100
2
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019

1
818
GANINA et al.
fugation, and the product was isolated by silica gel
1
00
column chromatography using petroleum ether as
eluent and dried under reduced pressure. The spectral
characteristics of compounds 5a–5g were in agreement
with published data [29, 46].
8
6
4
2
0
0
0
0
Cu-MOF
Cu-LSF
General procedure for the carboxylation of
terminal alkynes 6a–6e. An RLP25ML 25-mL glass
low-pressure reactor equipped with a gas inlet system,
pressure gage, and magnetic stirrer was charged with
0.15 mmol of alkyne 6a–6e, 0.30 mmol of Cs CO ,
Cu/Al SO3
2
0
1
2
3
Cycle no.
2
3
0
.0075 mmol of catalyst 1 or 3 or 5.6 mg of CuCa-LSF
Fig. 5. Fresh-start carboxylation of 4-methoxyphenylacety-
lene (6a) in the presence of catalysts 1–3.
(2), 0.225 mmol of butyl bromide, and 2 mL of DMF.
The reactor was filled thrice with CO , the gas pressure
was adjusted to 2 atm, and the mixture was stirred for
2
whereas the catalytic system based on low-silicon
faujasite worked better in the carboxylation of epox-
ides. In the carboxylation of alkynes, the cheaper cata-
lyst based on alumina-supported copper nanoparticles
is a worthy alternative to MOFs, since it provides
comparable results even at lower temperature.
1
6 h at 80°C (or at 60°C in the case of Cu/Al O ). The
2 3
mixture was then cooled to room temperature, and the
liquid part was separated by centrifugation, concen-
trated under reduced pressure, and analyzed by GLC or
1
H NMR (using DMSO-d or CDCl as solvent). The
6
3
product was isolated by silica gel column chromatog-
raphy using petroleum ether–ethyl acetate (20 : 1) as
eluent and dried under reduced pressure. The spectral
characteristics of compounds 7a–7e were in agreement
with published data [30, 34].
EXPERIMENTAL
Preparation of MOF HKUST-1. An authentic
sample of 1 was synthesized as described in [45].
Benzene-1,3,5-tricarboxylic acid (5.0 g), was dissolved
in 250 mL of EtOH–DMF (volume ratio 1 : 1) on
stirring with a magnetic stirrer. Copper(II) nitrate
trihydrate (10.387 g) was dissolved in 85 mL of
deionized water on stirring with a magnetic stirrer
FUNDING
This study was performed under financial support by the
Russian Foundation for Basic Research (project no. 18-29-
04030).
(
10 min, 25°C), and the copper(II) nitrate solution was
added to the solution of benzene-1,3,5-tricarboxylic
acid. The mixture was stirred for 24 h at 65°C. The
blue crystals of HKUST-1 were separated using
a laboratory centrifuge and washed first with DMF
and then with methylene chloride (3 × 12 mL) to
remove DMF from pores of the MOF. The light
turquoise crystalline solid was dried at 180°C for 4 h
and activated by heating for 16 h under reduced
pressure (~10–2 mm Hg) while gradually raising the
temperature from 25 to 150°C. As a result, the product
became dark violet.
CONFLICT OF INTERESTS
The authors declare the absence of conflict of interests.
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