URJC-1-MOF as New Heterogeneous Recyclable Catalyst for C-Heteroatom Coupling Reactions

Article abstract of DOI:10.1002/cctc.201900906

Guillermo Calleja and co-workers from @urjc describe URJC-1-MOF as a new heterogeneous recyclable catalyst for c-heteroatom coupling reactions. The capacity of copper-based URJC-1-MOF as a MOF catalyst in cross-coupling reactions has been evaluated, focusing on the Chan-Lam-Evans arylation-type reactions on amines and alcohols without extra additives or ligands. The extraordinary chemical and structural stability of URJC-1-MOF and its good specific surface, make this material a promising alternative to homogeneous Cu (II) catalysts for cross-coupling reactions. URJC-1-MOF showed a remarkable catalytic activity for cross-coupling C?N and C?O reactions, higher than other heterogeneous and homogeneous copper-based catalyst, such as CuO, HKUST-1, Cu?MOF-74, Cu(OAc)₂ and CuSO₄?5H₂O. Moreover, its easy recovery by simple filtration and reusability in successive runs without any loss of activity and stability, demonstrates the potential of URJC-1-MOF as an alternative catalyst for this kind of reactions in different chemical media of industrial interest.

Full text of DOI:10.1002/cctc.201900906

Accepted Article
Title: URJC-1-MOF as new heterogeneous recyclable catalyst for C-
Heteroatom coupling reactions
Authors: Antonio Muñoz, Pedro Leo, Gisela Orcajo, Fernando
Martinez, and Guillermo Calleja
This manuscript has been accepted after peer review and appears as an
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the VoR from the journal website shown below when it is published
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To be cited as: ChemCatChem 10.1002/cctc.201900906
Link to VoR: http://dx.doi.org/10.1002/cctc.201900906
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10.1002/cctc.201900906
ChemCatChem
COMMUNICATION
URJC-1-MOF as new heterogeneous recyclable catalyst for
C-Heteroatom coupling reactions
Dr. Antonio Muñoz,[a] Dr. Pedro Leo,[b] Dr. Gisela Orcajo,[a] Prof. Dr. Fernando Martínez, [b] and Prof. Dr.
Guillermo Calleja*[a]
metals [12], also difficult to recover. Among the procedures to form
Abstract: The capacity of copper-based URJC-1-MOF as a MOF
C-heteroatom bonds in cross-coupling reactions, without the need
catalyst in cross-coupling reactions has been evaluated, focusing on
of a precious metal catalyst, the use of Cu (I), Cu (II) or even Cu
the Chan-Lam-Evans arylation-type reactions on amines and alcohols
(0) shows particular interest. As an example, in the Ullmann-type
without extra additives or ligands. The extraordinary chemical and
coupling reaction, a copper source has been commonly used in
structural stability of URJC-1-MOF and its good specific surface,
stoichiometric amount in the presence of additional ligands,
make this material a promising alternative to homogeneous Cu (II)
catalysts for cross-coupling reactions. URJC-1-MOF showed a
remarkable catalytic activity for cross-coupling C-N and C-O reactions,
higher than other heterogeneous and homogeneous copper-based
catalyst, such as CuO, HKUST-1, Cu-MOF-74, Cu(OAc)2 and
CuSO4·5H2O. Moreover, its easy recovery by simple filtration and
reusability in successive runs without any loss of activity and stability,
demonstrates the potential of URJC-1-MOF as an alternative catalyst
for this kind of reactions in different chemical media of industrial
interest.
resulting in just moderate yields, requiring high temperatures and
long reaction times.[13] To face these difficulties some
modifications have been proposed, particularly for Chan-Lam-
Evans reactions, which include the use of arylboronic acids,
instead of arylhalides, and a nucleophile component, usually an
amine or an alcohol. This allows the use of the copper source in
catalytic amounts, just in the presence of an oxidant, usually
atmospheric oxygen which oxidizes the complex metal centers
from Cu (II) to Cu (III), favoring the oxidative addition catalyzed by
the metal center, as required for the coupling reaction to take
place according to the proposed mechanism. [14]
In this work, the copper-based URJC-1-MOF developed in our
research group[15] has been extensively tested as heterogeneous
catalyst in Chan-Lam-Evans-type coupling reaction, particularly,
in C-N and C-O coupling reactions, for a wide variety of substrates.
Different reaction conditions such as solvent, type of base,
temperature, reaction time and substrates have been studied,
observing the effect on the performance of URJC-1-MOF catalyst.
In addition, this material was compared with other copper-based
heterogeneous and homogeneous catalysts and its reusability
was also assessed in consecutive reaction cycles.
Introduction
Metal Organic Frameworks (MOFs) have emerged in the last
decades as a new class of porous materials with promising
properties for gas storage[1] and separation,[2] energy storage,[3]
drug delivery,[4] and catalysis.[5] These applications derive from
their porous structure with a remarkable pore volume and
extended surface area. Moreover, these materials provide a
widespread platform of tunable hybrid inorganic-organic
frameworks for the inclusion of specific metals with different
coordination environments and functional groups in the organic
Results and Discussion
linkers. So, MOF materials have
a great potential as
URJC-1-MOF catalyst used in this work has a crystalline structure
formed by Cu(II) linked to 1H-imidazol-4,5-tetrazole ligand,
displaying a BET surface area of 408 m2/g and a pore volume of
0.24 cm3/g. This material provides open metal sites as active
centers (see SI-1) and a remarkable thermal and chemical
stability for different organic solvents with different polarity, even
in boiling water. [15] This structural robustness contrasts with the
limited stability of other MOF materials shown in the literature.
This material has been tested as potential catalyst for C-
heteroatom coupling reactions using no additives nor precious
metals.[16]
heterogeneous catalysts in organic chemistry for different
synthetic transformations, becoming environmentally and
economically more efficient than classical homogeneous
catalysts, facilitating its implementation in multigram scale and
industrial scale processes.[6]. Some examples of these reactions
are cycloaddition reactions,[7] C-H bond amination reactions,[8]
multicomponent reactions,[9] and site-selective sp3 C-H
functionalization reactions such as undirected benzylic C-H
borylation, silylation and amination.[10] Of special interest are the
cross-coupling procedures for the formation of C-O and C-N
bonds in complex organic molecules.[11] Commonly, these
methodologies involve the use of homogeneous catalysis with
metallic complexes containing Ir, Pd, Rh and other high-cost
Initially, the influence of the type of solvent, base and temperature
was evaluated in the N-arylation and O-arylation of
benzeneboronic acid (1) with aniline (2) and phenol (3),
respectively. The reaction yields are listed in Table 1 (N-arylation)
and Table 2 (O-arylation). In general, the catalytic performance
were similar for both types of reactions. The coupling reaction
practically did not take place for non-polar solvents such as
dichloromethane, regardless of the type of the base (entries 1-3
of Table 1 and entries 1-4 of Table 2). Ethers like 1,4-dioxane and
THF also evidence a negligible activity of the URJC-1-MOF
material (entries 11-12 of Table 1 and Table 2).
[a]
[b]
Department of Chemical, Energy and Mechanical Technology,
Rey Juan Carlos University
C/ Tulipán s/n, 28933, Mostoles (Spain)
Department of Chemical and Environmental Technology,
Rey Juan Carlos University
C/ Tulipán s/n, 28933, Mostoles (Spain)
E-mail: guillermo.calleja@urjc.es
Supporting information for this article is provided through a link at
the end of the document.
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10.1002/cctc.201900906
ChemCatChem
COMMUNICATION
Table 1. Influence of solvent and base for aniline N-arylation reaction catalyzed
Table 2. Influence of solvent and base for phenol O-arylation reaction catalyzed
by URJC-1-MOF and comparison with other catalysts
[a]
by URJC-1-MOF and comparison with other catalysts [a]
Isolated
Yield (%)
Isolated
Yield (%)
Entry
Catalyst
Solvent
Base
Entry
Catalyst
Solvent
Base
CH Cl
1
URJC-1-MOF
CH Cl
no
__
1
2
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
no
__
2
2
2
2
2
2
2
2
2
[b]
trace
trace[b]
trace[b]
31
CH Cl
2
3
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
URJC-1-MOF
CH Cl
TEA
KOAc
TEA
TEA
2
2
CH Cl
CH Cl
3
KOAc
K CO
21
__
2
2
CH Cl
4
MeOH
MeOH
MeOH
EtOH
4
2
2
3
5
K CO
43
5
MeOH
MeOH
EtOH
TEA
18
2
3
6
KOAc
K CO
64
6
KOAc
K CO
39
7
62
7
56
2
3
2
3
8
EtOH
KOAc
67
8
EtOH
KOAc
K CO
41
72, 76[c]
75, 80[c]
trace[b]
trace[b]
9
DMF
K CO
70
9
DMF
2
3
2
3
84, 76[c]
trace[b]
__
10
11
12
13
DMF
KOAc
10
11
12
13
DMF
KOAc
1,4-Dioxane
KOAc
KOAc
K CO
1,4-Dioxane
KOAc
KOAc
K CO
THF
THF
[b]
74, 78[c]
[d]
URJC-1-MOF
URJC-1-MOF
71, 74[c]
DMF/H O
2
3
2
3
DMF/H O
2
2
[b]
79, 77[c]
[d]
73, 71[c]
__
14
URJC-1-MOF
KOAc
14
15
16
17
18
19
20
21
22
23
24
KOAc
DMF/H O
DMF/H O
2
2
15
16
CuO
CuO
DMF
KOAc
KOAc
__
__
CuO
DMF
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
[d]
[d]
CuO
__
DMF/H O
DMF/H O
2
2
17
18
Cu-MOF-74
Cu-MOF-74
DMF
KOAc
KOAc
48
Cu-MOF-74
Cu-MOF-74
HKUST-1
HKUST-1
Cu(OAc)2
Cu(OAc)2
CuSO4·5H2O
CuSO4·5H2O
DMF
40
[d]
17[e]
[d]
15[e]
27
DMF/H O
DMF/H O
2
2
19
20
HKUST-1
HKUST-1
DMF
KOAc
KOAc
21
DMF
[d]
13[f]
[d]
9[f]
DMF/H O
DMF/H O
2
2
21
22
Cu(OAc)2
Cu(OAc)2
DMF
KOAc
KOAc
76
63
DMF
72
[d]
[d]
70
DMF/H O
DMF/H O
2
2
23
24
CuSO4·5H2O
CuSO4·5H2O
DMF
KOAc
KOAc
62
56
DMF
65
[d]
[d]
69
DMF/H O
DMF/H O
2
2
[a] Reaction Conditions: Benzeneboronic acid 1 (1.5 eq), phenol 3 (1 eq),
catalyst (7.5mol% Cu), Base (2 eq), Solvent volume: 3 mL and RT.
Reaction time 15h [b]: Product observed in TLC, not isolated. [c]: Reaction
temperature 60ºC. [d]: Proportion DMF/H2O: 2/1. [e]: [Cu2+] in the leachate
= 8 ppm. [f]: [Cu2+] in the leachate = 71 ppm.
[a]: Reaction Conditions: Benzeneboronic acid 1 (1.5 eq), aniline 2 (1 eq),
catalyst (7.5mol% Cu), Base (2 eq), Solvent volume: 3 mL and RT. Reaction
time 15h [b]: Product observed in TLC, not isolated. [c]: Reaction
temperature 60ºC. [d]: Proportion DMF/H2O: 2/1. [e]: [Cu2+] in the leachate =
12 ppm. [f]: [Cu2+] in the leachate = 83 ppm.
Leaching of the catalytically active metal sites into the reaction
media along the reaction test, can partially induce the
homogenous catalytic reaction, so that the true heterogeneous
contribution of URJC-1-MOF catalyst should be checked (see SI-
2). The presence of water in the reaction medium was also tested
in order to assess the catalytic activity of URJC-1-MOF under a
more sustainable solvent. Additionally, the presence of humidity
In contrast, more polar solvents (methanol, ethanol and DMF) led
to higher product yields (entries 4-10 of Table 1 and 5-10 of Table
2). It is well-known that polar solvents can favor the stabilization
of the reaction intermediates, promoting their evacuation out of
the catalytic centers. Regarding the basic agent, the use of KOAc
improves significantly the catalytic activity of both C-heteroatom
coupling reactions for polar solvents. The maximum performance
was obtained with DMF, achieving remarkable yields of 84%
(Table 1, entry 10) and 75% (Table 2, entry 10) using KOAc as a
base and room temperature for aniline and phenol, respectively.
The increase of the reaction temperature up to 60ºC does not
significantly improve the yield of both reactions.
could favor the reduction of atmospheric oxygen, according to the
[17]
mechanism proposed by Hardouin et al.
The catalytic
experiments performed with a mixture of DMF/Water (2/1 volume)
hardly affects the activity achieved by DMF alone.
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For comparison purposes, other copper-based heterogeneous
Catalytic activity of URJC-1-MOF was also studied for N-arylation
and O-arylation reactions with different types of amine (Table 3)
and alcohol compounds (Table 4). All the resulting products were
isolated using flash chromatography on silica gel and
characterized with usual spectroscopic techniques (see SI-6).
Akyl and non-arylamines showed lower product yields than
arylamine substrates. A similar trend was also observed for non-
aromatic alcohols as compared to phenolic derivative substrates.
However, in both cases, the product yields (alkylamines: 2k, 53%
and 2l: 41%; non-arylamines: 2h, 71% and 2i, 69%; and non-
aromatic compounds: 3l, 56%, 3n, 42%, 3m, 67%, and 3o: 41%)
were significantly higher than those found in the literature, even
using homogeneous catalysts. [21]
(CuO, Cu-MOF-74[18] and HKUST-1[19]
) and homogeneous
catalysts (Cu(OAc)2 and CuSO4·5H2O) were tested using DMF,
KOAc as base and room temperature. URJC-MOF-1 displays a
higher activity than the heterogeneous system (Table 1 and 2;
entries 15, 17 and 19) and the homogeneous system (Table 1 and
2; entries 21 and 23). The basic and donor sites from the
tetrazole-based ligands of URJC-1-MOF and the unsaturated
copper acid sites seem to have a synergistic catalytic effect as
compared to the other MOFs with tereftalic derived ligands (Cu-
MOF-74 and HKUST-1) (see SI-4), copper oxide and
homogeneous copper salts. Additionally, the crystalline phase of
URJC-1-MOF, Cu-MOF-74 and HKUST-1 keeps unaltered (See
SI-4) and copper leached-off of the catalyst was not detected in
the reaction medium. Interestingly, unlike URJC-1-MOF, the
catalytic activity of heterogeneous CuO and MOF-type materials
(Table 1 and 2, entries 16, 18 and 20) in the presence of water
(DMF/water 2/1, KOAc as base and room temperature) showed a
lower activity and stability. Cu-MOF-74 and HKUST-1 evidenced
clear signals of structural damage of the framework (see SI-4) and
copper concentrations into the reaction media of 12 and 83 mg/L
for aniline arylation and 8 and 71 ppm for phenol arylation,
respectively. These results demonstrate the high robustness of
URJC-1-MOF in aqueous media compared to others MOFs.[20] In
the case of homogeneous catalytic systems (Table 1 and 2,
entries 22 and 24), the presence of water slightly reduced the
product yields.
In the case of substituted phenol compounds, meta- and para-
substituted compounds displayed higher product yields than the
ortho-substituted homologues (Table 4). These results seem to
indicate a certain chemo-selectivity of URJC-1-MOF, in particular
for bulky substituents, which has not been observed with other
heterogeneous catalyst such as (Cu(tpa)-MOF) using also polar
solvents and room temperature[22] or even with homogeneous
catalysts in Ullmann-type coupling reactions[21]
.
Table 4. O-arylation reactions between benzeneboronic acid (1) and different
alcohols at room temperature with URJC-1-MOF as catalyst.
Table 3. N-arylation reactions between benzeneboronic acid (1) and different
amines at room temperature with URJC-1-MOF as catalyst.
O-arylation products
N-arylation products
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This steric hindrance was evident for bulky functional groups such
as the tert-butyl group (3d (ortho-), trace; 3e (meta-), 71%; 3f
(para-), 70%) or the methoxy- group (3g (ortho-), 23%, 3h (meta-
), 59% and 3i (para), 62%). Interestingly, nitro-substituted
compounds evidenced the highest product yields in both N-
arylation and O-arylation reactions. This increase of reactivity of
nitro-substituted compounds was remarkable even for ortho-
nitroaniline (2d, 73%; Table 3).
URJC-1-MOF-MOF is stable in the presence of water, with no
copper leaching into the reaction media. URJC-1-MOF showed a
remarkable performance for N- and O-Arylation of
benzeneboronic acid with different aniline and phenol derivatives.
Its catalytic performance was sensitive to steric hindrance for
bulky molecules, showing an interesting chemo-selectivity for
arylation in meta- and para- positions. URJC-1-MOF was easily
recovered after reaction, maintaining its crystalline structure and
catalytic activity in successive reaction cycles. These results
make URJC-1-MOF a promising new catalyst, becoming a
greener and cheaper alternative to catalysts for coupling
reactions.
To evaluate the reusability of URJC-1-MOF catalyst, five
succesive reactions of aniline arylation to produce phenylaniline
(2a; Table 3) in gram-scale were carried out, with partial recovery
of the catalyst by simple filtration, washing with DMF, H2O and
EtOH and drying at 60 °C overnight. Concentration values were
fixed as: 7.5 mol of Cu (340 mg of catalyst), 1.05 g of
benzeneboronic acid (1), 0.535 g of aniline (2), 1.15 g of KOAc
and 35 mL of DMF. There was no significant loss of activity along
the five cycles of 15 hours of reaction, maintaining a product yield
above 90%. The X-ray diffraction patterns of recovered catalyst
after some cycles (first, third and fifth ones, Figure 1) evidenced
the stability of pristine URJC-1-MOF crystalline phase. Signals of
reactants and/or products retained in the URJC-1-MOF structure
were not detected from FT-IR spectra (see SI-5). Moreover, the
recovery of the solid catalyst after each cycle was practically total
(above 95 %). Finally, the copper leached-off was negligible,
showing liquid concentration values below 0.1 mg/L in the
reaction medium, as shown by ICP-OES measurements. All these
results confirmed the heterogeneous activity, chemical stability
and potential reusability of URJC-1-MOF in successive
consecutive reaction cycles.
Experimental Section
Typical catalytic tests to assess the activity of catalyst for N- or
O-Arylation
reactions,
characterization
technique
for
quantification of product yields and method for catalyst recovery
to evaluate the reusability in successive catalytic cycles are
described in SI-5. URJC-1-MOF and Cu-MOF-74 were
[15, 18]
synthesized following the procedure previously reported,
and HKUST-1 was purchased to Sigma-Aldrich (Spain).
Acknowledgements
The authors want to thank the Spanish Ministry of Science and
Innovation for the financial support to the Project (CTQ2015-
64526-P).
5º cycle (Yield = 90 %)
Keywords: heterogeneous catalysis • URJC-1-MOF• C-N coupling • C-O
coupling • Chan-Lam coupling
3º cycle (Yield = 91 %)
1º cycle (Yield = 92 %)
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10.1002/cctc.201900906
ChemCatChem
COMMUNICATION
This article is protected by copyright. All rights reserved.

10.1002/cctc.201900906
ChemCatChem
COMMUNICATION
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URJC-1-MOF is new copper-based
material that exhibits high activity in the
N and O‐ arylation reaction of aryl
boronic acids with amines and
alcohols. The catalyst can be facilely
separated and be reused without
significant degradation in catalytic
activity even in aqueous media.
Dr. Antonio Muñoz, Dr. Pedro Leo, Dr.
Gisela Orcajo, Prof. Dr. Fernando
Martínez and Prof. Dr. Guillermo
Calleja*
[Page No. – Page No.]
URJC-1-MOF as new heterogeneous
recyclable catalyst for C-Heteroatom
coupling reactions
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