One-Pot Preparation of Propargylamines Catalyzed by Heterogeneous Copper Catalyst Supported on Periodic Mesoporous Organosilica with Ionic Liquid Framework

Article abstract of DOI:10.1002/cplu.201500167

Copper supported on periodic mesoporous organosilica (PMO) with alkylimidazolium frameworks is a highly efficient and recoverable catalyst for the preparation of propargylamines through the three-component coupling reaction of aldehydes, alkynes, and amin

Full text of DOI:10.1002/cplu.201500167

DOI: 10.1002/cplu.201500167
Full Papers
One-Pot Preparation of Propargylamines Catalyzed by
Heterogeneous Copper Catalyst Supported on Periodic
Mesoporous Organosilica with Ionic Liquid Framework
Mohammad Gholinejad,* Babak Karimi,* Afsaneh Aminianfar, and Mojtaba Khorasani[a]
Copper supported on periodic mesoporous organosilica (PMO)
with alkylimidazolium frameworks is a highly efficient and re-
coverable catalyst for the preparation of propargylamines
through the three-component coupling reaction of aldehydes,
alkynes, and amines. The new catalyst is characterized using N2
adsorption/desorption analysis, transmission electron microsco-
py (TEM), energy dispersive spectroscopy (EDS), thermogravi-
metric analysis (TGA), diffuse reflectance infrared Fourier trans-
form spectroscopy (DRIFT-IR), and elemental analysis. The cata-
lyst is easily recovered by a simple filtration process and subse-
quently reused in the seven reaction cycles without any loss of
catalytic activity.
Introduction
Propargylamines are important synthons for the synthesis of
different nitrogen-containing pharmaceutical active compo-
nents and natural products such as b-lactams, peptides, iso-
steres, and agrochemicals.[1,2] Some propargylamines have
even been tested as targets for multifunctional drugs in the
treatment of Alzheimer’s and Parkinson’s diseases.[3]
small quantities of toxic metal catalyst from the product can
be considered a challenging issue.
Although various types of heterogenized copper catalysts
based on SiO2,[17] Fe3O4,[18] MCM-41,[19,20] montmorillonite,[21]
zeolites,[22] and mesoporous Cu/Al[23] have been developed for
A3 coupling reactions, the design of new catalytic systems with
concomitant mild reaction conditions as well as a low amount
of copper catalyst still poses many challenges. Moreover, to
the best of our knowledge, the A3 coupling reaction using
a supported copper catalyst based on periodic mesoporous or-
ganosilica (PMO) has not been reported.
Traditional methods for the preparation of propargylamines
include the reaction of less commercially available propargyl
halides with amines[4] or the use of stoichiometric amounts of
lithium or magnesium acetylides with imines.[5] However,
nowadays one important method to access propargylamines is
the transition-metal-catalyzed one-pot reaction of aldehydes,
amines, and alkynes. Different complexes and salts of transition
metals, such as iron,[6] zinc,[7] Cu/RuII bimetallic systems,[8] mer-
cury,[9] indium,[10] iridium,[11] gold,[12] silver,[13] nickel,[14] and
copper,[15] have been reported for this interesting reaction.
However, in comparison with the other transition metals,
copper is one of the best potential catalysts for the A3 cou-
pling reaction because copper catalyst precursors are usually
cheap, readily available, and less toxic, and have high reactivity
in A3 coupling reactions.[16]
Periodic mesoporous organosilicas (PMOs) are one of most
traditional organic–inorganic hybrid materials and have attract-
ed much research attention because of their mutual advantag-
es of the arrangement of organic and inorganic fragments
within the tunable pore wall and ordered mesoporous struc-
ture. PMOs with various mesostructures, morphologies, and
structures have been developed in the past few years, and
have shown unique properties in the field of catalysis.[24]
Recently, we reported gold nanoparticles supported on peri-
odic mesoporous organosilica with an ionic liquid framework
(PMO) as an efficient and recyclable catalyst for the three-com-
ponent coupling reaction of aldehydes, alkynes, and amines.[25]
Very recently, we also introduced agarose-supported copper
nanoparticles as an efficient catalyst for the three-component
click synthesis of 1,2,3-triazoles in water.[26] In continuation of
our interest in PMO and heterogeneous copper-catalyzed reac-
tions, herein, we wish to disclose the synthesis and characteri-
zation of a copper catalyst supported on PMO and its applica-
tion as a heterogeneous catalyst in the A3 coupling reaction of
amines, aldehydes, and alkynes under low copper loading and
mild reaction conditions.
Despite the high efficiency in some of the reported transi-
tion metal catalysts for A3 coupling reactions, the majority of
reported catalytic systems include homogeneous systems, and
suffer from the recovery and recycling of the catalyst from the
reaction mixture. In particular, because the A3 coupling reac-
tions have been applied extensively in the synthesis of phar-
maceutically active compounds, it seems that the separation of
[a] Dr. M. Gholinejad, Prof. B. Karimi, A. Aminianfar, Dr. M. Khorasani
Department of Chemistry
Institute for Advanced Studies in Basic Sciences (IASBS)
P. O. Box 45195-1159, Gava zang, Zanjan 45137-6731 (Iran)
E-mail: gholinejad@iasbs.ac.ir
karimi@iasbs.ac.ir
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cplu.201500167.
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Results and Discussion
Table 1. Physical and chemical properties of PMO-IL, Cu@PMO-IL, and recovered cata-
lyst.
The PMO-IL was synthesized through the hydrolysis
and polymerization of 1,3-bis(3-trimethoxysilylprop-
yl)imidazolium chloride and tetramethylorthosilicate
in the presence of Pluronic P123 as a structure-direct-
ing agent in acidic medium, according to our last
synthetic reports.[25] The catalyst denoted as
Cu@PMO-IL was also prepared through the direct re-
action between copper chloride (CuCl2) and chloride
ions of the imidazolium moieties in the PMO-IL. Then,
the resulting materials were characterized by various
well-known techniques.
Material
SBET
Vt
DBJH
% C[d] % N[d] Loadingof FG
[a]
[b]
[m2 gÀ1
]
[cm3 gÀ1
]
[cm][c]
[mmolgÀ1
]
PMO-IL
Cu@PMO-IL
Re-Cu@PMO-IL 427
559
470
1.12
0.98
0.93
10.6
10.6
10.6
16.7
15.0
15.4
3.3
3.0
3.1
1.16 (IL)
1.12 (IL), 0.7 (Cu)
1.11 (IL), 0.6 (Cu)
[a] SBET =specific surface area derived from linear part of adsorbed nitrogen in the
range 0.05 to 0.3. [b] Vt =total pore volume derived from adsorbed nitrogen from rel-
ative pressureꢀ0.99. [c] DBJH =pore size distributions calculated from the adsorption
branch using BJH method. [d] Calculated using elemental analysis (CHN); estimated
by TG, elemental analysis, AAS, and ICP techniques.
The N2 adsorption/desorption isotherms and pore
size distributions for both PMO-IL and Cu@PMO-IL are shown
in Figure 1. The PMO-IL exhibited a typical type IV isotherm
with H1 hysteresis loop, according to the IUPAC classifica-
tion.[27] A sharp capillary condensation step at the relative pres-
sure 0.8 indicated the formation of highly ordered organofunc-
tionalized mesostructures. Furthermore, the BET calculations
showed the successful formation of PMO-IL with a high surface
area of 559 m2 gÀ1, which contained open mesoporous chan-
nels with a total pore volume of 1.12 cm3 gÀ1 (Table 1). More-
over, the pore size distributions calculated from the adsorption
branch using the BJH method (Figure 1B) displayed highly uni-
form mesopores centered on 10.6 nm. In contrast, the surface
area and total pore volume for Cu@PMO-IL were determined
to be 470 m2 gÀ1 and 0.98 cm3 gÀ1, respectively (Table 1). The
remarkable decrease in surface area and pore volume for the
catalyst in comparison with the parent PMO-IL could be con-
sidered as further evidence for the successful immobilization
of active catalyst species into the PMO-IL scaffold. Additionally,
the narrowed pore size distributions of the catalyst indicate
that its structural order remained intact after modification of
the parent PMO-IL with copper precursors (Figure 1B).
The TEM image of PMO-IL demonstrated the formation of
a highly ordered two-dimensional hexagonal mesostructure
(Figure 2). Furthermore, the TEM image of Cu@PMO-IL provid-
ed further confirmation that the ordered mesostructures of the
PMO-IL scaffold were well retained during the catalyst prepara-
tion process. All the data are also in good agreement with the
N2 sorption analysis (Table 1).
In addition, the presence of Cu was also confirmed by
energy dispersive spectroscopy (EDS); the catalyst exhibited
three distinct peaks at approximately 1, 8, and 9 keV (Figure 3).
Figure 1. A) N2 adsorption/desorption isotherms and B) pore size distribu-
tions for PMO-IL and Cu@PMO-IL.
Figure 2. TEM images of PMO-IL (top) and Cu@PMO-IL (bottom).
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Figure 3. EDX image of Cu@PMO-IL.
The presence of bridged ionic liquids in the framework was
confirmed by using the diffuse reflectance infrared Fourier
transform spectroscopy (DRIFT) technique. PMO-IL (see Fig-
ure A, Supporting Information) and the catalyst (Figure B, Sup-
porting Information) exhibited similar patterns. The peak at
2958 cmÀ1 corresponds to the CÀH stretching of propyl func-
tional moieties in the samples.[28] The presence of ionic liquids
can be also confirmed by the peak at around 1634 cmÀ1 that
relates to the stretching vibration of C=N bonds.[29] Moreover,
imidazolium rings can be confirmed in the band at 1560 cmÀ1,
which corresponds to the stretching vibration of C=C bonds.[29]
Finally, the stretching vibration of OÀH in surface silanol
groups appeared at around 3400 cmÀ1.[30] The aforementioned
peaks clearly indicate that the bridged ionic liquids remained
intact during the mesostructure formation and surfactant ex-
traction stages.
Figure 5. Thermogravimetric analysis of Cu@PMO-IL.
The coordination geometry of the copper ion was studied
by diffuse reflectance UV/Vis spectroscopy (DR UV/Vis)
(Figure 6). The sample showed an absorption band at 220 nm,
which was ascribed to the imidazolium cation. Besides this
band, for Cu@PMO-IL, two other peaks were observed at 290
and 400 nm, which were assigned to the CuCl4 species.[31] It
2À
could be deduced that the copper ion was introduced to the
2À
materials through the formation of a CuCl4 complex. Hence,
the loading of ionic liquid in the materials was calculated to
be 1 mmolgÀ1, which was further confirmed by elemental anal-
ysis (Table 1). Finally, the copper content in the Cu@PMO-IL
was determined to be 0.7 mmolgÀ1 by using atomic absorp-
tion spectroscopy (AAS) and induced coupled plasma (ICP)
techniques.
Thermogravimetric analysis (TGA) of PMO-IL and the catalyst
was achieved in the temperature range 20 to 6008C under air
flow (Figures 4 and 5). The TG patterns showed a weight loss
of approximately 3–6% in the range 20 to 1008C, which could
be correlated to the desorption of water and ethanol remain-
ing from the solvent extraction process. The absence of any re-
markable weight losses from around 100 to 3008C also indicat-
ed that the used surfactant was carefully washed in the extrac-
tion process. Furthermore, the samples displayed major weight
losses of 20% at 300–5008C, which could be attributed to the
loss of bridged ionic liquid precursors from the material net-
works.
After the initial characterization of Cu@PMO-IL, we investi-
gated the possibility of Cu@PMO-IL as a heterogeneous cata-
lyst in the A3 coupling of amines, aldehydes, and alkynes. The
A3 coupling of benzaldehyde, piperidine, and phenylacetylene
was first selected as a model reaction, and the effect of sol-
vents and reaction temperature were evaluated in this model,
and for a best comparison all reactions were performed within
24 h. The study indicated that in the different solvents (tolu-
ene, CH3CN, CHCl3, 1,4-dioxane, DMSO, H2O, and also solvent-
free conditions), the best result was obtained using 0.15 mol%
Figure 6. DRS-UV/Vis spectra of PMO (black), CuCl2 (red), CuCl42À (blue), and
Figure 4. Thermogravimetric analysis of PMO-IL.
Cu@PMO-IL (violet).
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Table 2. Screening of different solvents for the reaction of benzaldehyde,
phenylacetylene, and piperidine.[a]
Entry
Solvent
T [8C]
Yield [%][b]
1
2
3
4
5
6
7
8
toluene
toluene
CH3CN
1,4-dioxane
CHCl3
DMSO
H2O
solvent-free
60
100
60
60
60
60
100
60
33
63
10
32
Figure 7. Recyclability of Cu@PMO-IL during A3 coupling of benzaldehyde,
piperidine, and phenylacetylene.
97
trace
trace
12
Some analyses were performed to show the recyclability and
stability of the catalyst. The N2 adsorption/desorption analysis
indicated that the recovered catalyst showed no change in
nanostructure during catalysis progression, and the surface
[a] Reaction conditions: benzaldehyde (1 mmol), piperidine (1.3 mmol),
phenylacetylene (1.2 mmol), Cu@PMO-IL (0.15 mol%), and 2 mL solvent
for 24 h. [b] Yield of isolated product. DMSO=dimethyl sulfoxide.
area and pore volume decreased to 427 m2 gÀ1 and 0.9 cm3 gÀ1
,
catalyst in CHCl3 at 608C (Table 2, entry 5). Interestingly, this
finding is in good agreement with our previous report.[25] En-
couraged by this promising result, the amount of copper cata-
lyst was optimized. In this regard, it was found that the desired
propargylic amine was obtained in 55 and 34% isolated yields
in the presence of 0.1 and 0.05 mol% catalyst, respectively;
the results showed that 0.15 mol% of catalyst was the most
suitable amount for this reaction.
respectively (Figure C, Supporting Information). Remarkably,
the average pore size of the recovered catalyst was essentially
retained, which shows the high hydrothermal stability of the
catalyst. Also, leaching of copper species after seven runs was
determined by ICP analysis to be 2.8%, confirming the stability
of the heterogeneous catalyst during the reaction. Moreover,
the TG pattern of the recovered catalyst indicated that the cat-
alyst compositions were stable under the reaction conditions
used (Figure D, Supporting Information). Also, the DRIFT-IR
spectra of the recovered catalyst showed that all of the func-
tional groups were stable and no destruction was observed
during the reaction (Figure E, Supporting Information).
With these optimized conditions, the generality of our cata-
lytic system was also checked in the reaction of phenylacety-
lene with various aldehydes in the presence of either piperi-
dine or morpholine (Table 3). Remarkably, the A3 coupling of
benzaldehyde, phenylacetylene, and morpholine proceeded to
the related product in 96% yield under optimized reaction
conditions (Table 3, entry 2). Moreover, the results indicated
that various aldehydes containing either electron-releasing or
-withdrawing groups such as Me, OMe, iPr OPh, Br, and Cl, can
also furnish the related propargylic amines in good to excel-
lent yields (Table 3, entries 3–11). 2-Chloro benzaldehyde, as
a relatively sluggish substrate, also afforded the corresponding
propargylamines in excellent yields (Table 3, entries 12, 13).
Moreover, the presented catalyst showed high activity with
regard to aldehydes comprising a heteroaryl moiety. Thus, 2-
thiophen carbaldehyde gave the expected propargylamine in
93% yield (Table 3, entry 14). Interestingly, heptanal, as a chal-
lenging aliphatic aldehyde, furnished the desired product in
excellent yield (Table 3, entry 15). Finally, this reaction was also
successful for the coupling of 1-naphthaldehyde with both pi-
peridine and morpholine and phenylacetylene as the carbon
nucleophile partner, affording the corresponding propargylic
amines in excellent yields (Table 3, entries 16, 17).
The proposed mechanism for the reaction is the same as the
well-known mechanism for the A3 coupling reaction
(Scheme 1). CÀH activation of the alkyne by the copper cata-
lyst produces copper acetylide. Then, copper acetylide reacts
with the iminium ion produced from the reaction of aldehyde
and amine, resulting in the formation of a propargylamine
with regeneration of the copper catalyst.[32]
A comparison of the catalytic activity of presented catalyst
with some other heterogeneous copper catalysts in the A3 cou-
We also studied the possibility of recycling the catalyst for
the reaction of benzaldehyde with piperidine and phenylacety-
lene. The results of this study showed that the catalyst is recy-
clable; seven runs with recycling of the catalyst showed a negli-
gible decrease in catalytic activity (Figure 7).
Scheme 1. Proposed mechanism for A3 coupling reaction.
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Table 3. Reactions of structurally different aldehydes with amines and phenylacetylene.[a]
Yield [%][b] Entry ArCHO
Entry ArCHO
R2NH Product
R2NH Product
Yield [%][b]
1
97
96
10
11
97
2
3
98
98
99
88
94
96
82
12
13
14
15
16
17
4
5
6
7
97
93
94
89
86
8
9
87
93
[a] Reaction conditions: aldehyde (1 mmol), piperidine or morpholine (1.3 mmol), phenylacetylene (1.2 mmol), Cu@PMO-IL (0.15 mol%), and 2 mL CHCl3 for
24 h. [b] Yield of isolated product.
pling of benzaldehyde, morpholine, and phenylacetylene are
presented in Table 4. The results indicate that with Cu@PMO-IL
as the catalyst, the reaction affords an excellent isolated yield
under comparable and mild reaction conditions.
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Synthesis of ionic liquid precursor
Table 4. Comparison of catalytic activity of Cu@PMO-IL with other heter-
ogeneous copper catalysts in A3 coupling reaction.
The ionic liquid precursor was prepared with a few modifications
to our last synthetic reports.[24b] In a typical method, a suspension
of sodium imidazolide in dry THF was prepared from the reaction
of dried imidazole (2 g) and NaH 95% (0.77 g) at a flame-dried
two-necked flask containing dry THF (60 mL) under argon. Trimeth-
oxysilane (5.4 mL) was added and the mixture was heated at reflux
for 30 h. Then, the reaction mixture was cooled to room tempera-
ture and the THF phase removed under reduced pressure until an
oily compound was obtained. Subsequently, 3-chloropropyltrime-
thoxysilane (5.4 mL) and dry toluene (60 mL) were added and the
mixture was heated at reflux for 48 h until an insoluble ionic liquid
was obtained in the toluene. The toluene phase was removed, and
the ionic liquid phase containing NaCl remained. Then, dry CH2Cl2
was added for the precipitation of NaCl. The resulting CH2Cl2
phase was transferred to another well-dried two-necked flask, and
the organic solvent was removed under reduced pressure until the
ionic liquid and unreacted starting materials were obtained. Finally,
the ionic liquid was washed with dry toluene to remove the start-
ing materials.
Catalyst
Mol% cat. T [8C] Yield [%][b]
Silica-CHDA-Cu[17]
Cu(OH)x-Fe3O4
CuNPs/TiO2
Cu0-Mont.[21]
1
80
120
70
110
90
92[a]
99
91
90
96
84
71
[18]
0.1
0.5
0.05
0.6
1.1
2
[15j]
[15g]
GO-CuCl2
CuNPs/MagSilica[15n]
SiO2-NHC-CuI[15]
100
RT
MCM-TSCuI[19]
3
80
92
[Cu(N2S2)]Cl-Y[15h]
3
3
0.15
70
110
60
90
Polymer-anchored copper (II) complex[15i]
Cu@PMO-IL
82[a]
96
[a] With piperidine. [b] Yield of isolated product.
Conclusion
In summary, copper supported on periodic mesoporous orga-
nosilica with alkylimidazolium frameworks (Cu@PMO-IL) was
found to be an efficient catalyst for A3 coupling of aldehydes,
amines, and phenylacetylene in the presence of a low amount
of copper and under mild reaction conditions. The catalyst was
characterized by using suitable analyses such as EDS, TEM,
TGA, and DRIFT-IR, as well as N2 adsorption/desorption analysis
and elemental analysis. The catalytic system showed high ac-
tivity for the one-pot coupling of phenylacetylene, piperidine,
or morpholine with various aldehydes, including those contain-
ing electron-donating (Me, OMe, iPr, and OPh) or -withdrawing
groups (Cl and Br), sterically hindered (2-substituted), aliphatic
(Heptanal), and heteroatom (thienyl) species under the same
reaction conditions. Moreover, the catalyst could be reused at
least seven times without significant loss of catalytic activity.
Synthesis of PMO-containing ionic liquid, PMO-IL
PMO-IL was synthesized according to our latest methods. In a typi-
cal procedure, Pluronic P123 (1.67 g) was dissolved in a mixture of
H2O (10.5 g) and HCl (2m, 46.14 g). Then, KCl (8.8 g) was added
and the system was stirred until a homogenous solution was ob-
tained. A premixture of ionic liquid (0.86 g) and tetramethoxyor-
thosilicate (2.74 g) in dry methanol was added to the aforemen-
tioned solution and stirred at 408C for 24 h. The resulting mixture
was aged without stirring at 1008C for 72 h. The obtained PMO
with surfactant was filtered, washed with deionized water, and
dried at room temperature. The surfactant was extracted from the
PMO-IL by a Soxhlet apparatus by using ethanol (100 mL) and c-
HCl (3 mL). In a typical extraction, the as-synthesized PMO (1 g)
was washed four times with acidic ethanol over 12 h.
Preparation of Cu@PMO-IL
Experimental Section
Cu@PMO-IL was prepared through the direct reaction of copper (II)
chloride and imidazolium moieties in the PMO-IL.[28] In a typical
procedure, PMO-IL (0.5 g, 1.1 mmolgÀ1) was added to acetonitrile
(10 mL) and sonicated for at least 10 min. CuCl2 (0.15 g, 0.88 mmol)
as the Cu precursor (already dissolved in 2 mL acetonitrile) was
added gradually to the aforementioned suspension, and the mix-
ture was stirred under reflux conditions for 24 h. The resulting
system was filtered and washed with acetonitrile (3”10 mL) and
acetone (2”10 mL), respectively. The resulting yellow solid, denot-
ed as Cu@PMO-IL, was dried at 508C.
General
Thin-layer chromatography was performed on silica gel 254 analyti-
cal sheets. Column chromatography was performed on silica gel 60
Merck (230–240 mesh) in glass columns (2 or 3 cm diameter) using
1
15–30 grams of silica gel per gram of crude mixture. The H and
13C NMR spectra were recorded at 400 MHz and 100 MHz, respec-
tively, in CDCl3 using TMS as internal standard. Thermogravimetric
analysis (TGA) was conducted from room temperature to 8008C in
an oxygen flow with a NETZSCH STA 409 PC/PG instrument. The
structures of the prepared materials were observed by transmis-
sion electron microscopy (FEI Tecnai 12 BioTWIN), and were verified
further by nitrogen adsorption/desorption analysis (BELsorp-max
(Japan)). Energy dispersive spectroscopy (EDS) was performed with
a Carl Zeiss ÆiGMA instrument. The compounds were analyzed for
C, H, and N with an elemental analyzer system (varioEL CHNS).
DRS-UV/Vis spectra were obtained with a PerkinElmer Lambda 25
instrument. The copper content in the catalyst was determined by
atomic absorption spectrometry (Varian). DRIFT-IR spectra were re-
corded with a Bruker Vector 22 instrument after mixing the sam-
ples with KBr.
General procedure for A3 coupling reaction
The catalyst (2 mg, 0.7 mmolgÀ1 Cu) was added to a mixture of al-
dehyde (1 mmol), phenylacetylene (1.2 mmol), and amine
(1.3 mmol) in chloroform (2 mL), and the solution was stirred at
608C for 24 h. After completion of the reaction, the solvent was
evaporated under reduced pressure. The crude product was ob-
tained by column chromatography (EtOAc, n-hexane) to afford
propargylamines in good to excellent yields. The known products
were confirmed by 1H NMR and 13C NMR spectroscopy.
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Acknowledgements
We are grateful to the Institute for Advanced Studies in Basic Sci-
ences (IASBS) Research Council.
Keywords: copper · heterogeneous catalysis · mesoporous
materials · multicomponent reactions · propargylamine
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Manuscript received: April 19, 2015
Revised: June 17, 2015
Final Article published: July 14, 2015
ChemPlusChem 2015, 80, 1573 – 1579
www.chempluschem.org
1579
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