Polymer supported copper(II) amine-imine complexes in the C-N and A3 coupling reactions

Article abstract of DOI:10.1002/aoc.3847

New polymer supported Cu(II) complexes based on an epoxy functionalized gel type resin were prepared using the multi-stage procedures. The reactions of epoxy groups with ethylenediamine or tris(2-aminoethyl)amine, and then NH₂ groups with salic

Full text of DOI:10.1002/aoc.3847

Received: 3 February 2017
DOI: 10.1002/aoc.3847
Revised: 23 March 2017
Accepted: 25 March 2017
F U L L PA P E R
Polymer supported copper(II) amine‐imine complexes in the C‐N
3
and A coupling reactions
Agnieszka Bukowska
| Wiktor Bukowski | Karol Bester | Krzysztof Hus
Faculty of Chemistry, Rzeszów University of
Technology, Powstańców W‐wy 6, 35‐959
Rzeszów, Poland
New polymer supported Cu(II) complexes based on an epoxy functionalized gel
type resin were prepared using the multi‐stage procedures. The reactions of epoxy
groups with ethylenediamine or tris(2‐aminoethyl)amine, and then NH groups with
2
Correspondence
Agnieszka Bukowska, Faculty of Chemistry,
Rzeszów University of Technology,
Powstańców W‐wy 6, 35‐959 Rzeszów,
Poland
salicylaldehydes were used for the preparation of a series of amine‐imine function-
alized polymer supports. Copper(II) acetate was used as a source of metal ions. The
complexes were characterized using ICP‐OES, FTIR, DR UV–Vis and TGA
3
Email: abuk@prz.edu.pl
techniques, and tested as catalysts in two model C‐N and a series of A coupling
reactions. Their catalytic activity was rather low in the C‐N coupling reactions
between imidazole and iodobenzene or phenylboronic acid. However, the second
of the reactions could be conducted effectively under milder conditions. The
3
complexes were efficient used as recyclable catalysts in the A coupling reactions.
A series of aromatic aldehydes and secondary amines and phenylacetylene could
be coupled using 1% mol catalyst.
KEYWORDS
3
A coupling reactions, C‐N coupling reactions, polymer supported copper catalysts
1
| INTRODUCTION
Diamine ligands turned out to be particular useful in this
[
19]
field.
The meaning of C‐N coupling reactions in organic
The copper‐mediated coupling reactions play a very
synthesis increased when the new, more reactive arylation
[1–11]
[1,8]
important role in organic synthesis.
The first two types
agents were proposed.
Boronic acids and their derivatives
of C‐N coupling reactions were discovered by Ullman and
seem to be the most universal reactant among them due to
tolerating a wide variety of functional groups. Presently, not
[12]
Goldberg more than 100 years ago.
Aryl halides and
[
20–28]
[29,30]
[29]
aromatic amines or amides were then used as reactants,
respectively. Initially, the C‐N coupling reactions could be
performed using the stoichiometric amounts of copper or
copper salts and the harsh reaction conditions. The first
catalytic variant of C‐N coupling reactions was reported by
only amines
carbamides, carbamates,
different N‐heterocycles
and amides,
but also imides,
[
29,31]
[29,32]
sulphoamides,
and
[
32–43]
can be used as the reactants
being a source of nitrogen nucleophiles in the C‐N coupling
reactions with boronic acids or its derivatives. Thanks to this,
many valuable compounds used for the production of
pharmaceuticals, agrochemicals, polymers and advanced
materials can be obtained.
[
13]
Goldberg in 1906.
Unfortunately, due to the low activity
of the catalysts used in the initial stage of research, the
practical meaning of C‐N coupling reactions in organic
synthesis was limited for several next decades. The formation
of C‐N bonds became much easier when the active palladium
catalytic systems were developed by the groups of Buchwald
The multicomponent coupling reactions occurring
3
between aldehydes, amines and terminal alkynes (A coupling
reaction) are another useful transformation catalyzed by the
homogenous and heterogeneous systems bearing copper
[
14–18]
and Hartwig,
on the one side, and it was found that the
[
11,44]
ligation of copper ions by some polydentate ligands improved
ions.
The reactions are a synthetic source of
[1–5]
significantly their catalytic activity,
on the other hand.
propargylamines which are also the important intermediates
Appl Organometal Chem. 2017;e3847.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 15
https://doi.org/10.1002/aoc.3847

2
of 15
BUKOWSKA ET AL.
for the synthesis of biological active compounds used as the
2 | EXPERIMENTAL
2.1 | General remarks
[11,44–46]
components for pharmaceuticals,
protectants (herbicides and fungicides).
and plant
[47]
Despite the large progress made in the catalytic variants of
3
All the chemicals used in this work for the preparation of
polymer supported copper amine and amine‐imine complexes
and in the performed catalytic studies were purchases from
Aldrich, Merck or Fluka, and used as received, unless other-
wise stated. Unsaturated monomers (styrene, divinylbenzene
and glycidyl methacrylate) were purified from inhibitors
by extraction with an aqueous solution of 5% NaOH and
20% NaCl.
FTIR spectra were recorded using an FTIR Nicolet iN10
MX microscope equipped with a FTIR micro‐compression
diamond cell. Samples for the microanalysis were prepared
by flattening several polymer beads between a pair of
diamond windows placed in the micro‐compression cell.
Diffuse reflectance UV–Vis–NIR spectra were recorded in
solid state using a Jasco V‐670 spectrophotometer equipped
with a Jasco ISN‐723 UV–Vis NIR 60 mm integrating sphere
C‐N and A coupling reactions, the need in developing the
new catalytic systems for these transformations remains still
topical. Currently, the heterogeneous catalytic systems seem
to arouse the particular interest of researchers due to the
simplicity of their isolation and re‐use. Several examples of
[
22,48–56]
the heterogeneous copper catalysts active in the C‐N
and A
3
[57–61]
coupling reactions were described previously.
Different inorganic materials (e.g. fluoroapatite,
[
48]
[
26,49,50]
[22,32,39,51,52]
[54,55]
silica,
biopolymers (e.g. cellulose,
supports for the copper catalysts.
), organic polymers,
including
) were tested as
[53]
chitosan
The immobilization of copper ions on the surface of
porous polymer particles or inside of the particles of
nonporous polymer gels can be easily performed using
different donor groups attached to the polymer chains. For
instance, Chiang and Olsson were used the polystyrene
bearing β‐ketoester groups for the preparation of the
polymer‐supported copper catalyst capable of catalysing the
cross‐coupling reactions between different N‐ or O‐containing
and BaSO as a standard.
4
1
13
H–NMR and C–NMR spectra were recorded in
chloroform‐d using a 500 MHz Bruker Avance spectrometer.
TGA analysis was performed using a METTLER
TOLEDO TGA/DSC 1 analyser. Samples were heated from
[22]
substrates and arylboronic acids.
The examples of the
polymer supported copper catalysts for the C‐N, C‐O and
C‐S cross‐coupling reactions were also described by Islam
2
5 to 600 °C (10 °C/min) in nitrogen atmosphere (50 ml
[
39,62,63]
N
2
/min).
et al.
They synthesized the polymer anchored Cu(II)
[39]
ICP OES analyses were performed at λ = 324,754 nm
using a Horiba Jobin Yvon Optima 2 ICP‐OES spectrometer.
The samples of polymer supported complexes (about
complexes bearing the moieties of glycine
based Schiff base.
and a furfural
The polymer catalysts developed by
[
63]
this group were tested in the C‐N coupling reactions in which
aryl iodides, aryl bromides, and boronic acids were used as
arylation agents, and anilines, benzylamine, imidazole,
phenols and tiophenols as nucleophilic reactants. Kodicherla
et al. described the use of the polymer supported copper
catalyst based on the polystyrene bearing N,N‐
5
(
–10 mg) were mineralized in the concentrated nitric acid
5.0 ml) using a Plazmatronika Uni Claver II microwave
mineralizer.
SEM measurements were performed using a HITACHI
S‐3400 N scanning electron microscope (FEI) equipped with
a tungsten cathode operating at 20 kV.
[
64]
dimethylethylenediamine as ligating groups.
The catalyst
3
GC analyses were performed using an Agilent 7890 GC
chromatograph equipped with a split‐splitless injector, a
flame ionization detector, an auto‐sampler and a HP‐5
capillary column. The analytical solutions were prepared by
dissolving 10 mg of reaction mixtures in 0.5 ml THF with
nonane as a standard.
GC MS analyses were conducted using an Agilent 7890
GC chromatograph equipped with a split‐splitless injector, a
MS detector, an auto‐sampler and a HP‐5 + MS capillary
column.
was applied successfully in the A coupling reactions
between a series of aromatic aldehydes, secondary amines
and phenylacetylene. It could also be recovered quantitatively
by simple filtration and reused without a significant loss of its
[
64]
catalytic activity.
Quite recently, Islam et al. described the
use of polymer supported copper(I) complex bearing glycine
3
[65]
moieties as an efficient catalyst of A coupling reactions.
In the presence of the developed catalyst, the reactions could
be performed in water without using any additives or
hazardous organic solvents.
Herein, we reported on the catalytic activity of the new
polymers supported amine‐imine copper(II) complexes
prepared in our laboratory based on the epoxy functional-
ized polymer gel which was developed by our group and
2.2 | Preparation of polymer supported
copper(II) complexes
2.2.1 | Preparation of polymer supports
[66]
synthesized as described previously.
They were
explored as catalysts in two model C‐N and a series of
A coupling reactions.
The GMA resin bearing 1.4 mmol epoxy groups per gram
was used as starting material. It was synthesized as described
3

BUKOWSKA ET AL.
3 of 15
in Ref. [66] using glycidyl methacrylate (GMA, 20 mol.‐%),
styrene (S, 77 mol.‐%) and divinylbenzene (DVB, 3 mol.‐%).
The appropriate amine functionalized resins abbreviated as 1
and 2 were obtained in the reaction of the GMA resin with an
excess of ethylenediamine (EDA) or tris(2‐aminoethyl)amine
heated to 70 °C, or other indicated temperature, and stirred
at this temperature for the time indicated. The progress of
the reaction was monitored using gas chromatography.
The final reaction mixture was diluted with ethyl acetate
and water (1:1 v/v). The catalyst was filtered off, washed with
small portions of water and ethyl acetate and dried under
lowered pressure. The collected organic phase was extracted
with water to remove inorganic impurities and dried with
anhydrous magnesium sulfate. The coupling product was
isolated by precipitation and identified using GC MS.
The recycling experiments with catalyst 3‐Cu were
performed at 110 °C in DMSO.
(TAEA), respectively, in DMF at 80 °C, similarly to Ref.
[67]. Amine‐imine functionalized resins 3 and 4 were derived
from resins 1 and 2, respectively, as follows. The appropriate
amine resin was swelled with methylene chloride (10 ml per
1
gram) in a 50 ml PP syringe equipped with a cotton filter, a
Luer valve, and a rubber septum with a needle. The appropri-
ate salicylaldehyde dissolved in the mixture of methylene
chloride and methanol (1:1 v/v) was then added to the
swelled resin. The syringe was then sealed with the septum
and placed on a vibrating shaker. The reaction mixture was
shaken at ambient temperature for 24 hrs. The final polymer
product was rinsed several times with the solvent used as a
reaction medium to remove unreacted aldehydes. The pres-
ence of aldehyde residuals in filtrates was monitored using
TLC.
2
.3.2 | Coupling reaction of phenylboronic
acid and imidazole
Imidazole (1 eq.), phenylboronic acid (1.5 eq.), K CO (2 eq.),
2
3
or other indicated bases, and the appropriate copper catalyst
(0.05–0.2 eq.) were mixed with DMF, or other indicated
solvent, in a 5 ml vial equipped with a Teflon‐coated
cross‐shaped magnetic stir bar. The vial was then sealed with
a screw cap with a septum and placed in a StarFish®
Multi‐Experiment Work Station. The heterogeneous reaction
The resulting polymer particles bearing amine‐imine
units were yellow in color.
o
mixture was heated to 60 or 70 °C and reacted for the time
2
.2.2 | Preparation of polymer supported
indicated. The progress of the reaction was monitored using
gas chromatography. The final reaction mixture was treated
similarly as in the case of the reactions between aryl halides
and imidazole.
In the similar manner, a series of catalytic experiments
under base‐free conditions was conducted.
Cu(II) complexes
The appropriate resin bearing amine‐imine units was swelled
with methylene chloride (10 ml/g) in a PP 50 ml syringe
equipped with a cotton filter and a Luer valve. The solution
of copper(II) acetate monohydrate (1 eq.) in methanol, prepared
separately in a 5 ml vial, was then added dropwise to the
swelled resin. MeOH and CH Cl were used for the reaction
The recycling experiments with catalyst 4.3‐Cu was
performed at 70 °C in EtOH.
2
2
in the ratio of 1:1 v/v. The reaction mixture was shaken at ambi-
ent temperature for 24 hrs. The final polymer supported Cu(II)
3
2
.3.3 | A coupling reactions between
complex was rinsed several times with 1:1 v/v MeOH‐CH Cl2
2
aldehydes, amine and phenylacetylene
mixture and dried under reduced pressure at 40 °C.
The complexes derived from resins 3 and 4 were green in
color. The loadings of Cu(II) ions in the prepared complexes
were determined using ICP‐OES.
The appropriate aldehyde (1 eq.), amines (1.2 eq.),
phenylacetylene (1.5 eq.) and the appropriate copper catalyst
0.01 eq.) were mixed with 0.5 ml 1,4‐dioxane, or other indi-
(
cated solvent, in a 5 ml vial equipped with a Teflon‐coated
cross‐shaped magnetic stir bar. The vial was then sealed with
a screw cap with a septum and placed in a StarFish® Multi‐
Experiment Work Station. The reaction mixture was heated
to 80 °C and reacted for the time indicated. The progress of
the reaction was monitored using gas chromatography. The
final reaction mixture was diluted with ethyl acetate and the
catalyst was filtered off. The resulting organic solutions were
concentrated. The crude product was purified by column
chromatography on silica gel using the mixtures of hexane
and ethyl acetate as an eluent. The final product was
2
.3 | Catalytic tests
2
.3.1 | Coupling reactions between aryl
halides and imidazole
The appropriate aryl halide (ArX, 1 eq.) and imidazole (IMD,
1.5 eq.) were dissolved in DMSO, or other indicated solvent,
in a 5 ml vial equipped in a Teflon‐coated cross‐shaped
magnetic stir bar. The appropriate copper complex (0.1 eq.)
and K CO (2 eq.), or other indicated base, were then added
to the resulting solution. The vial was sealed and then it was
placed in a StarFish® Multi‐Experiment Work Station
equipped with a stirring hotplate. The reaction mixture was
2
3
1
13
characterized by H–NMR, C–NMR and FT‐IR.
The recycling experiments with catalyst 3‐Cu were
conducted at 100 °C in 1,4‐dioxane.

4
of 15
BUKOWSKA ET AL.
3
| RESULTS AND DISCUSSION
.1 | Catalyst preparation and
the ranges characteristic of epoxy ring stretches (905 and
−1
8
40 cm ), on the other hand. The new absorption band at
−1
3
about 1630 cm and the changes in absorption intensity at
the ranges attributed to NH and OH stretching vibrations, found
in the spectrum of 4.1 in relation to the spectrum of 2, proved
that the condensation step also occurred effectively resulting
in converting primary amine groups to salicylaldimine moie-
ties. For polymers 4.3 and 4.4, the absorption bands at the
characterization
It is well‐known that the ligation of copper ions can influence
advantageously on their activity in promoting the C‐N
coupling reactions.
[
1]
Thus, it was expected that the
complexing of copper(II) ions by the N,N,O chelating ligands
bearing the moieties of ethylenediamine (EDA) or tris(2‐
aminoethyl)amine (TAEA) condensed with salicylaldehyde
and immobilized onto a swellable polymer gel will enable us
to obtain the new catalytic systems for the coupling reactions.
To prepare the appropriate amine‐imine functionalized
polymer supports, the GMA gel developed previously in
our laboratory was first treated with an excess of EDA or
TAEA, similarly as in Ref. [67]. Resins 1 and 2 were pro-
duced as a consequence (Scheme 1). The resulting amine
functionalized resin were characterized by the nitrogen per-
centage of 3.5 and 5.7, respectively. It means that their beads
regions characteristics of NO group stretching vibrations
2
−1 [68]
(1660–1490, 1390–1260 and 870–700 cm )
were also
found in the spectra (Figure 1S ES). This finding was additional
proof of the condensation reaction of NO ‐substituted
2
salicylaldehydes with NH groups of resins 2.
2
Finally, the amine‐imine functionalized polymers were
contacted with a solution of copper(II) acetate to obtain a
series of polymer supported Cu(II) complexes (Scheme 1).
The mixture of methanol and methylene chloride, in the ratio
of 1:1 v/v, were used to swell the beads of the amine‐imine
functionalized polymers. It facilitated the interactions
between the N,N,O‐ligating groups anchored to the polymer
matrix (also those groups located inside the polymer beads)
and Cu(II) ions from the solution. As a result, the polymer
supported complexes 3‐Cu and 4‐Cu loaded with
0.54–0.91 mmol/g were obtained (Table 1).
consisted of about 1.25 and 2.05 mmol NH groups per gram.
2
Resin 1 and 2 were then used for the synthesis of two addi-
tional polymer supports, abbreviated as 3 and 4, in the reac-
tions of condensation with the appropriate salicylaldehydes
(Scheme 1).
The FTIR spectra of the resulting polymers revealed that
the immobilization of Cu(II) ions on the amine‐imine
functionalized supports occurred simultaneously with acetate
counter‐ions. It could be concluded based on the strong
absorption bands at about 1530 and 1310 cm− which
appeared in the spectrum of 4.1‐Cu (Figure 1). Furthermore,
the changes in absorption intensity at the range of
3000–2100 cm− observed for 4.1‐Cu compared with 4.1
seemed to prove that the phenolic OH groups of the units
of salicylaldehyde take part in complexing Cu(II) ions.
Each stage of the modification of polymer particles was
confirmed by FT‐IR spectroscopy. Figure 1 presents the
FTIR spectra of the GMA resin and some products derived
from it – resins 2 and 4.1. The ring opening of epoxy groups
occurring under the influence of EDA or TAEA molecules
resulted in appearing in the spectra of the resulting polymers
the broad absorption band corresponding to N‐H and O‐H
1
1
−1
stretching vibrations (3600–2300 cm ), on the one hand,
and in diminishing in the intensity of absorption bands at
SCHEME 1 Preparation of polymer
supported copper(II) complexes

BUKOWSKA ET AL.
5 of 15
FIGURE 1 Representative FTIR spectra of the GMA gel, polymers 2 and 4, and polymer supported complex 4.1‐Cu
TABLE 1 Copper ion loadings of the polymer supported complexes
Abbr.
% Cu*
mmol/g Cu
3
4
4
4
4
4
4
‐Cu
5.1
5.8
4.1
3.4
3.8
5.8
5.2
0.80
0.91
0.64
0.54
0.60
0.91
0.81
.1‐Cu
.2‐Cu
.3‐Cu
.4‐Cu
.5‐Cu
.6‐Cu
*
Determined using ICP‐OES
The polymer supported copper(II) complexes were also
characterized using DR‐UV–Vis spectroscopy, thermogravi-
metric analysis and scanning electron microscopy.
FIGURE 2 Comparison of the DR UV–vis spectra of copper(II)
acetate, polymer 4.1 and complex 4.1‐Cu
Figure 2 presents the electronic spectra recorded for cop-
per(II) acetate and polymers 4.1 and 4.1‐Cu(II). The coordi-
nation of Cu(II) ions to the amine‐imine ligands anchored on
resin 4.1 resulted in obtaining the spectrum with very compli-
cated nature due to overlapping the bands attributed to d‐d
transitions of Cu(II) ions being in the pseudo‐octahedral
Figure 4 shows the SEM images registered for the beads
of the starting GMA resin and the final complex 4.1‐Cu.
It can be easily concluded that the nonporous gel‐type
morphology of GMA beads did not change in a conse-
quence of their multi‐stage chemical modification.
[
68]
environment
with π‐π* transition of salicylaldimine
moieties.
The TGA analysis of complex 4.1‐Cu revealed that only
about 5% weight loss was observed when the complex was
heated from 25 to 200 °C. Probably, it was caused by the
desorption of the physically absorbed molecules of the
solvents used for the preparation of the complex. The rate
of weight loss became clearly faster only above 200 °C
3.2 | Catalytic tests
3.2.1 | Reactions of aryl halides with imidazole
Polymer supported copper(II) complexes 3‐Cu was first
tested as a catalyst in the coupling reaction between
imidazole and iodobenzene (Scheme 2) under the conditions
similar to those described in Ref. [56] (1 eq. iodobenzene,
(Figure 3) and it achieved maximum at 405 °C.

6
of 15
BUKOWSKA ET AL.
1
.5 eq. imidazole, 2 eq. K CO in DMSO at 110 °C). The
2
3
catalyst was applied in the amount of 10 mol.‐% Cu(II) ions
in relation to iodobenzene. The effect of several other
solvents on the activity of 3‐Cu in the model coupling
reaction was then studied. The obtained results were collected
in Table 2.
DMSO turned out to be clearly better as a medium for
performing the reaction than other solvents used in the
experiments. The yield of N‐phenylimidazole (PIMD) in
DMSO amounted to 87% after 24 hrs. The satisfactory yield
was also observed for two amide solvents – DMF and NMP.
In butanol and diglyme, the yields of PIMD were clearly
lower. Complex 3‐Cu was inactive catalytically in toluene.
The activity of 3‐Cu in the coupling reaction between
imidazole and iodobenzene in DMSO increased when
Cs CO , K PO or KOH were used as a base instead of
FIGURE 3 Thermogravimetric curve recorded for 4.1‐Cu
2
3
3
4
K CO . For the best of them, Cs CO , the yield of PIMD
2
3
2
3
of 96% after 5 hrs. Was obtained. In the case of the use of
KOH, the yield of PIMD was only slightly lower ‐ 94% after
5
hrs. The use of NEt as a base gave the result clearly worse
3
than for K CO .
2
3
The catalytic activity of complexes 3‐Cu and 4‐Cu in the
coupling reaction between imidazole and iodobenzene was
then compared. A series of experiments were conducted in
DMSO using KOH as a base. There were not observed
significant differences in the activity of the complexes
TABLE 2 Results of the coupling reaction between imidazole and
iodobenzene in the presence of 3‐Cu and 4‐Cu
a
Catalyst
Base
Solvent
Time, h
Yield, %
‐
KOH
DMSO
DMSO
24
24
Nr
87
3
‐Cu
2 3
K CO
nd
48
8
87(2 run)
rd
4
70 (3 run)
K
K
K
K
K
K
2
CO
CO
CO
CO
CO
CO
3
DMF
24
24
24
24
24
24
5
8
5
24
74
Traces
19
65
38
87
94
88
96
2
2
2
2
2
3
3
3
3
3
Toluene
Diglyme
NMP
Butanol
DMSO
DMSO
DMSO
DMSO
DMSO
KOH
PO
CO
NEt
K
3
4
Cs
2
3
3
50
4
.1‐Cu
.1‐Cu
.2‐Cu
.3‐Cu
.5‐Cu
K
2
CO
3
DMSO
DMSO
DMSO
DMSO
DMSO
8
5
5
5
5
91
96
88
85
89
4
KOH
KOH
KOH
KOH
FIGURE 4 SEM images of GMA gel (up) and 4.1‐Cu (down)
4
4
4
a
Determined based on GC analysis. nr – no reaction.
Reaction conditions: imidazole (0.375 mmol), iodobenzene (0.25 mmol), base
(0.5 mmol) in solvent (1 ml), temperature 110 °C.
SCHEME 2 Reaction of iodobenzene with imidazole

BUKOWSKA ET AL.
7 of 15
TABLE 3 Comparison of the activity of 4.1‐Cu in the reaction of iodobenzene with imidazole to the activity of the copper heterogeneous catalytic
systems described previously
o
Catalyst
Base/solvent
Temp. C
Time h
Yield of PIMD, %
Ref.
Cell‐Cu(0) (0.05 g)
K
K
2
CO
CO
3
3
/DMSO
130
25
12
6
95
99
92
92
[53]
[52]
[24]
[49]
Polyaniline‐Cu nanofiber (5 mol %)
PANI‐Cu (polyaniline) (2.5 mol %)
Silica immobilized Cu‐Schiff base
2
/DMF, N
2
Cs
Cs
2
CO
3
/CH
3
CN, N
2
80
12
8
2
CO
3
/toluene, N
2
100
(
pyridine 2‐carboxyaldehyde) (5 mol %)
Polymer supported
p[(C N = CHPy]Cu(OAc)
Polymer supported Cu Schiff base (0.05 g)
Cu O (10 mol %)
Cu‐Y‐zeolite (10.5 mol %)
.1‐Cu (10 mol %)
K
K
2
CO
CO
3
/DMSO
120
14
93
[62]
6
H
4
2
(1.56 mol %)
2
3
/DMSO, N
2
120
110
120
12
24
24
95
99
99
[63]
[69]
[70]
2
KOH/DMSO
CO /DMF
KOH/DMSO
CO /DMSO
K
2
3
4
110
110
5
8
96
91
This
Work
K
2
3
bearing EDA and TAEA units condensed with
salicylaldehyde, although, complex 4.1‐Cu allowed to
obtain PIMD with the yield slightly higher than 3‐Cu.
When the complexes bearing the moieties of substituted
salicylaldehydes, both the electron donor (Me, 4.2‐Cu)
time twice. In the third reaction run, the yield of ~70% was
achieved after 48 hrs. A decrease in the activity of the
recovered catalyst resulted mainly from the partial
TABLE 4 Results of the reaction of imidazole with phenylboronic
acid in the presence of 3‐Cu and 4‐Cu
and electron acceptor (NO , 4.3‐Cu and F, 4.5‐Cu) groups,
2
were used in the reaction, the yield of PIMD decreased
below 90%. This finding seems to indicate that the addi-
tional substituents in the units of salicylaldehyde play rather
a secondary role in the activation of Cu(II) ions in the C‐N
coupling reaction between imidazole and iodobenzene.
Complex 3‐Cu was also used as a catalyst in the reactions
of imidazole with bromobenzene and chlorobenzene. Under
the same reaction conditions (KOH, 110 °C, DMSO),
bromobenzene was converted into PIMD with the yield of
a
Catalyst
‐Cu
Base
Solvent
Time, h
Yield of PIMD, %
3
K
2
CO
3
EtOH
EtOH
24
10
38
100
‐
4.1‐Cu
K
K
2
CO
CO
‐
3
3
DMSO
EtOH
EtOH
Toluene
3
CH CN
24
24
12
24
24
24
24
24
30
63
90
Traces
33
2
K
K
K
K
2
CO
2
CO
2
CO
2
CO
3
3
3
3
3
i‐PrOH
MeOH
CH Cl
59
40% after 24 hrs. The coupling reaction was not observed
b
49
c
for chlorobenzene.
2
K CO
traces
2
2
It is difficult to conclude on the activity of the complexes
developed in our laboratory in view of the results published
by other groups on the use of heterogeneous catalysts in the
coupling reactions of imidazoles with aryl halides. The best
of our catalysts (complex 4.1‐Cu) seems to be more active
than the catalysts described in Ref. [69,70], and probably in
Ref. [52,63]; unfortunately, the authors of Ref. [52,63] did
not deliver any information on the concentration of the cata-
lysts used. The rest of the catalysts presented in Table 3
seems to be more active in the C‐N coupling reaction of
iodobenzene and imidazole than 4.1‐Cu.
4
.2‐Cu
.3‐Cu
K
2
CO
‐
3
EtOH
EtOH
24
24
9
12
4
K
2
CO
3
EtOH
12
5
24
48
48
92
‐
‐
‐
‐
100
nd
100 (2 run)
rd
78 (3 run)
th
73 (4 run)
4
.4‐Cu
K
2
CO
‐
3
EtOH
EtOH
EtOH
EtOH
EtOH
12
7
90
100
91
4
4
4
.5‐Cu
.6‐Cu
.6‐Cu
K
K
2
CO
CO
‐
3
3
12
12
8
2
85
The possibility of the reuse of 3‐Cu in the coupling
reaction between imidazole with iodobenzene was also
examined. A series of experiments were conducted in DMSO
100
a
Determined based on GC analysis.
using K CO as a base. It was found that the recovered
2
3
Reaction conditions: imidazole (0.25 mmol), phenylboronic acid (0.375 mmol),
catalyst showed the activity significantly lower than the fresh
one. In the second reaction run the same yield of PIMD
base (0.5 mmol), 0.2 eq. cat, solvent (1 mL), temperature ‐ 70 °C.
b
Temperature ‐ 60 °C.
c
(about 85%) was obtained only after lengthening the reaction
Temperature ‐ 40 °C.

8
of 15
BUKOWSKA ET AL.
decomposition of the polymer catalyst occurred under reac-
tion conditions. In a consequence, the leaching of copper ions
from the heterogeneous catalyst to the reaction mixture was
observed; a decrease of about 50% in the loading of Cu(II)
ions was noted for the catalyst recovered after the third use.
Furthermore, the comparison of the FTIR spectra of the fresh
beads of 3‐Cu and the recovered ones revealed a decrease in
absorption intensity at the ranges characteristic of the
stretching vibrations of C=O (ester) and C=N
Different solvents were explored as a potential medium
for performing the coupling reaction between imidazole and
phenylboronic acid in the presence of 4.1‐Cu. The reactions
were conducted at 70 °C using 2 eq. K CO and 20 mol.‐%
2
3
4.1‐Cu. The best result was obtained for ethanol (64% PIMD,
24 hrs.). The use of i‐PrOH gave the product with the slightly
less yield (59%, 24 hrs). When methanol was used as a
reaction medium, PIMD was formed with the yield of ~50%
after 24 hrs. The yield of PIMD was rather unsatisfactory
when DMSO or acetonitrile were used. The experiments in
toluene and CH Cl gave the C‐N coupling product in the
(
salicylaldimine) groups, respectively at 1725 and
−
1
1670 cm . These findings indicated that the cleavage of
2
2
C‐O and C=N bounds, respectively in the ester and amine‐
imine units, under the influence of an inorganic base might
be probably responsible for the observed loss of Cu(II) ions
and, in consequence, a dramatic decrease in the activity of
the recovered catalyst. The degradation of the polymer
supported catalyst intensified when KOH was used as a base.
trace amounts.
Using ethanol as a reaction medium and K CO as a base,
2
3
the catalytic activity of complexes 3‐Cu and 4‐Cu was
compared. Complex 3‐Cu bearing EDA moieties condensed
with salicylaldehyde molecules was found as significantly
less active than 4.1‐Cu, based on TAEA and SA. In the
presence of 3‐Cu, PIMD was formed with the yield of 38%
only after 24 hrs. A significant improvement in the catalytic
3
.2.2 | C‐N coupling reaction between
phenylboronic acid and imidazole
The catalytic activity of 3‐Cu and 4‐Cu was next evaluated in
the C‐N coupling reaction between imidazole and
phenylboronic acid (Table 4, Scheme 3). The impact of
reaction conditions and catalyst structure on the yield of
PIMD was analyzed.
3
SCHEME 4 A coupling reaction
SCHEME 3 Reaction of phenylboronic acid with imidazole
SCHEME 5 Homocoupling of phenylacetylene
3
TABLE 5 Results of the A coupling reaction in the presence of 3‐Cu and 4‐Cu
o
a
b
Catalyst
‐Cu
Solvent
Temperature, C
Time, h
Yield of BA, %
Yield of DPBD %
3
‐
80
80
80
80
80
80
80
60
80
60
80
24
24
24
24
24
24
24
24
24
30
24
96
92
73
73
57
99
64
10
73
11
79
21
4
5
14
1
9
8
2
8
11
15
3
CH CN
DMSO
DMF
Ethylene glycol
,4‐dioxane
EtOH
MeOH
i‐PrOH
THF
1
Toluene
4
4
4
.1‐Cu
.2‐Cu
.5‐Cu
.6‐Cu
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
80
80
80
80
24
24
24
24
95
93
98
95
8
10
10
9
4
a
b
,
Determined based on GC analysis.
Reaction conditions: benzaldehyde (1 mmol), piperidine (1.1 mmol), phenylacetylene (1.2 mmol), 1 mol.‐% cat in solvent (0.5 ml).

BUKOWSKA ET AL.
9 of 15
TABLE 6 Synthesis of propargylamines from aldehydes, amines, and phenylacetylene using 3‐Cu as a catalyst
a
Aldehyde
Amine
Product
Time, h
Yield of aldehyde, %
1
0/24
82/100
1
0/24
86/90
1
1
0/24
0/24
92/97
75/80
1
0/24
80/89
1
1
1
0/24
0/24
0/24
73/77
81/89
42/55
1
0/24
79/97
(Continues)

1
0 of 15
BUKOWSKA ET AL.
TABLE 6 (Continued)
a
Aldehyde
Amine
Product
Time, h
Yield of aldehyde, %
1
0/24
50/91
1
1
0/24
0/24
89/96
72/87
a
Determined based on GC analysis.
Reaction conditions: aldehyde (1 mmol), amine (1.1 mmol), phenylacetylene (1.2 mmol), 1%‐mol 3‐Cu in 1,4‐dioxane (0.5 ml), temperature ‐ 80 °C.
activity was observed for the complexes bearing electron
The polymer supported copper amine‐imine complexes
described in this work were undoubtedly active as catalysts
in the coupling reaction of imidazole with phenylboronic
acid. Their catalytic activity was improved under base‐free
reaction conditions. However, the observed activity was
lower than the activity of the other heterogeneous catalysts
acceptor (F or NO ) substituents. The yield of PIMD for com-
2
plexes 4.3–4.6‐Cu increased to about 90% after 12 hrs. The
worst result was obtained for complex 4.2‐Cu based on 2‐
methyl‐substituted salicylaldehyde. The yield of PIMD in
this case was below 10% after 24 hrs.
[
39,48]
[24,33,39,48,49,53]
Previously, the groups of Islam and Kantam
described previously.
described the possibility of conducting the C‐N coupling
reaction between imidazole and phenylboronic acid under
base‐free conditions. We also decided to conduct a series of
similar experiments with the Cu(II) complexes developed in
our laboratory. The additional experiments were conducted
at 70 °C using ethanol as a reaction medium. The obtained
results were collected in Table 4. It turned out that in the
3
3
.2.3 | A coupling reactions
The multicomponent coupling reactions between aryl
aldehydes, secondary amine and phenylacetylene were the
third type of coupling reactions in which the catalytic activity
of complexes 3‐Cu and 4‐Cu were examined (Table 5,
Scheme 4). The reactants were used in the molar proportion
1:1.1:1.2, similarly, for instance, to Ref. [60]. Different
solvents were first tested as a potential medium for conducting
the reaction between benzaldehyde, piperidine and
phenylacetylene in the presence of 1 mol.‐% 3‐Cu. Additional
experiments were also performed under solvent‐free
conditions and in the absence of the catalyst. Except the
experiments including methanol and THF which were
performed at 60 °C, the others were conducted at 80 °C.
absence of K CO3 a significant improvement in the
2
catalytic activity of the developed polymer supported Cu
(
II) complexes was observed in the most cases. As a result,
PIMD could be formed with the quantitative yield within 5–
0 hrs. Complex 4.3‐Cu bearing the moieties of 5‐fluoro‐
1
substituted salicylaldehyde proved to be the most active
under base free‐conditions. Only a slight improvement in
the catalytic activity was found for complex 4.2‐Cu bearing
2‐methylsalicylaldehyde moieties.
3
Complex 4.3‐Cu was reused three times under base‐free
To monitor the progress of A coupling reactions and to
conditions. It was found that its activity diminished during
the reuse in the reaction. In a consequence, the yield of PIMD
identify the reaction products we used GC and GC–MS anal-
yses, respectively. The occurrence of two parallel coupling
reactions was observed under the applied reaction conditions.
Beside the desired propargylamine, 1,4‐diphenylbutadiyne
(DPBD) was found in the reaction mixtures as a side product.
The homo‐coupling of phenylacetylene (Scheme 5) occurred
st
decreased from 100% in the 1 run after 5 hrs., to 73% noted
th
for the 4 run after 48 hrs. It was found that a decrease in the
activity of the catalyst after recovering resulted mainly from
gradual liberating copper ions to the solution under applied
reaction conditions.
3
parallel to the A coupling reaction.

BUKOWSKA ET AL.
11 of 15
It is well known that both Cu(I) and Cu(II) ions are able to
activate of terminal acetylenes in the cross‐coupling reactions
[71]
as well as to catalyze its homocoupling.
The appropriate
homocoupling reactions are named Glaser and Eglinton
[
71,72]
couplings.
Hence, the symmetrical diacetylenes are
found as by‐products of copper catalyzed reactions including
3
[73,74]
terminal acetylenes, e.g. in A coupling,
coupling
Sonogashira
[
75]
[76]
and click reactions.
Based on the chromatograms obtained for different
reaction time the relative changes in the concentrations of
all the substrates and the desire (propargylamine) and side
(diacetylene) coupling products could be observed. The best
yield of the appropriate propargylamine was found for the
reaction in 1,4‐dioxane. However, the yield obtained under
solvent‐free conditions was only slightly less. The other
solvents, except acetonitrile, gave the results clearly worse.
Using acetonitrile, the yield of the appropriate
propargylamine was also relatively high and it amounted to
above 90%. The lowest yield of the reaction was obtained
using methanol and THF. However, in the case of the use of
3
FIGURE 5 Reuse of 3‐Cu in the A coupling reaction of
benzaldehyde, piperidine, phenylacetylene
3
these two solvents, the A coupling reaction was performed
at 60 °C. The presence of the appropriate propargylamine
was not detected in the reaction mixture obtained for
the blank experiment performed using 1,4‐dioxane, even
after 24 hrs. Although, the traces of the appropriate
propargylamine and DPBD were found after the same
time when the reaction between benzaldehyde, piperidine
and phenylacetylene was carried out under solvent free
conditions.
The amount of DPBD formed parallel in the
homocoupling reaction depended on the solvent used for
3
performing the A reaction (Table 5). The least DPBD (1%)
3
in the final reaction mixture was found when the A coupling
3
FIGURE 6 Heterogeneity test in the A coupling of benzaldehyde,
morpholine and phenylacetylene
reaction was conducted in ethylene glycol and the most (21%)
under solvent‐free conditions. For 1,4‐dioxane, the amount of
DPBD amounted to 9% and it was similar to those observed
for ethanol and 2‐propanol. However, the latter solvents
3
provided the much lower yield of the A coupling product
than the former. The relatively high amount of DPBD in the
final reaction mixtures was found when toluene or THF were
used as a reaction medium, respectively 15 and 11%. For
THF, the amount of the by‐product was comparable to the
yield of the propargylamine.
The activity of complexes 4‐Cu were examined at 80 °C
using the same model reactants as in the case of complex
3‐Cu and 1,4‐dioxane as a reaction medium (Table 5). When
the complexes bearing the ligating groups based on TAEA
and salicylaldehyde units were applied as catalysts, there
was observed slight worsening of the yield of propargylamine
compared to the result obtained for 3‐Cu. The activity of the
polymer supported copper complexes with TAEA units was
not improved rather when the amine units were additionally
condensed with the units of substituted salicylaldehydes,
3
FIGURE 7 Tentative mechanism for the A coupling reaction
catalyzed by the polymer supported copper(II)

1
2 of 15
BUKOWSKA ET AL.
3
independently of the presence of electron donor (3‐Me,
successfully four times in the A coupling reaction
between piperidine, benzaldehyde and phenylacetylene in
1,4‐dioxane at 100 °C. Admittedly, the activity of the
recovered catalyst diminished clearly after the first use,
however, it was unchangeable in the next four reaction
cycles (Figure 5).
4
.2‐Cu) or electron acceptor groups (5‐F, 4.5‐Cu and 3,5‐F,
F, 4.6‐Cu). All the catalysts bearing TAEA units provided
the appropriate propargylamine with the yield of above 90%
(
after 24 hrs).
3
Catalyst 3‐Cu was also applied successfully in the A
coupling reactions including different substituted benzalde-
hyde and three other secondary amines (Table 6). All the
performed reactions gave the appropriate propargylamines
An additional hot filtration test was also conducted for
3‐Cu in the reaction between benzaldehyde, morpholine,
and phenylacetylene at 100 °C using 1,4‐dioxane as a
solvent (Figure 6). The heterogeneous catalyst was filtered
off from the reaction mixture after 100 minutes when the
conversion of the aldehyde amounted to about 50%. The
reaction was continued with the filtrate for next 200 minutes.
Some progress of the reaction could be detected after this
3
with the good or very good yields. The A coupling products
1
were isolated and characterized using FTIR, H ‐NMR and
1
3
C ‐NMR (see ESI).
The experiments with the catalyst recovered from the
reaction was also performed. Catalyst 3‐Cu was reused
TABLE 7 Comparison of the activity of 3‐Cu in the reaction between benzaldehyde, piperidine and phenylacetylene to the activity of heteroge-
neous copper catalytic systems described previously
Catalyst (mol%)
Reaction conditions
Yield of propargylamine, % Catalyst recycling
Ref.
Toluene, reflux, 6 h
85
5
[64]
(3)
H
2
O, reflux, 6 h
95
10
[65]
(0.6)
Copper(II) carboxymethylcellulose (5)
Neat, 100 °C, 15 h
Neat, 80 °C, 12 h
81
95
4
[77]
[79]
15
(1)
Neat, 70 °C, 4 h
91
10
[80]
(2)
(
5)
Cu(0)‐Montmorylonit (0.05)
Cu nanoparticles (NPs) supported on graphene (1) Toluene, 100 °C, 24 h
H
2
O, reflux, 10 h
86
94
96
95
88
4
3
4
5
7
[81]
[59]
[78]
[82]
[83]
Toluene, reflux, 3 h
Cu(I)‐modified zeolites (7)
Neat, 80 °C, 15 h
Toluene, 80 °C, 5 h
(3)
1
,4‐dioxane, 80 °C, 24 h
99
4
This work
(1)
I – salicylaldehyde, CH
2
Cl
2
, rt; II – salicylaldehyde or derivatives, CH
2
Cl
2 2 2 3
, rt; III – copper(II) acetate, CH Cl :CH OH 1:1 v/v, rt.

BUKOWSKA ET AL.
13 of 15
time. This finding indicated that the catalytically active
homogenous species appeared in the reaction mixture.
Probably, a part of copper ions, particularly the ions
which were bound weaker with the support, was released
to solution under relatively harsh reaction conditions.
Using ICP‐OES analysis it was found that, the leaching
of copper ions from the catalysts during its first use
amounted to about 15 wt.%. The further progress of the
reaction was not observed when the hot filtration test
was repeated for the recovered catalyst (in the second
run). In the second run, the leaching of copper ions to
solution was below 1 wt.%.
and iodobenzene or phenylboronic acid. However, their
relatively high catalytic activity in the A coupling reactions
3
between phenylacetylene and a series of benzaldehydes and
secondary amines was observed. Although, a clear decrease
in the catalytic activity of 3‐Cu, resulting from partial
leaching copper ions from the polymer support to the
solution, was observed after its first use, the activity of the
polymer supported catalyst remained on the same satisfying
level in the next four reaction runs.
ACKNOWLEDGMENTS
Based on the obtained results and the results published
The authors thank to Dr. Bogdan Myśliwiec from Laboratory
of Spectrometry, Faculty of Chemistry, Rzeszow University
of Technology for recording the NMR spectra of
propargylamines, and Dr Maciej Pytel from Faculty of
Mechanical Engineering and Aeronautics, Rzeszów
University of Technology for carrying out the ICP‐OES
analyses.
[
59,71,77,78]
3
previously,
the tentative mechanism of A coupling
reaction in the presence of the developed polymer supports
amine‐imine copper(II) complex was proposed (Figure 7).
According to this mechanism, phenylacetylene interacts with
the Cu(II) complex forming initially a π‐complex which
undergoes deprotonating under influence of amine. The
activated alkenyl complex reacts then with the iminium ion
formed in the reaction of aldehyde with secondary amine.
As a result, the appropriate propargylamine is produced and
the Cu(II) catalyst is regenerated. The homocoupling reaction
path is also probable for the di‐nuclear Cu(II) acetylide
complex. It leads to DPBD as a side product.
REFERENCES
[1] S. V. Ley, A. W. Thomas, Angew. Chem. Int. Ed. 2003, 42, 5400.
[2] J. Haider, K. Kunz, U. Scholz, Adv. Synth. Catal. 2014, 346, 717.
[3] D. Ma, Q. Cai, Acc. Chem. Res. 2008, 41, 1450.
Table 7 presents results obtained previously for the
model reaction of piperidine, benzaldehyde and
phenylacetylene in the presence of different heterogeneous
copper catalysts. Due to the differences in the reaction
conditions applied in this work and in the most cited
articles there was difficult to conclude clearly on the rela-
tive activity of the polymer supported Cu(II) complexes
described in this work in relation to the activity of the
catalytic systems described previously. However, the activ-
ity of catalyst 3‐Cu seems to not diverge significantly from
the activity of the best catalyst presented in Table 6. It also
seems to be comparable with the activity of the homoge-
[
[
[
4] G. Evano, N. Blanchard, M. Toumi, Chem. Rev. 2008, 108, 3054.
5] F. Monnier, M. Taillefer, Angew. Chem. Ind. Ed. 2009, 48, 6954.
6] E. Sperotto, G. P. M. van Klink, G. van Koten, J. G. de Vries,
Dalton Trans. 2010, 39, 10338.
[
[
[
7] Y. Liu, J.‐P. Wan, Org. Biomol. Chem. 2011, 9, 6973.
8] K. S. Rao, T.‐S. Wu, Tetrahedron 2012, 68, 7735.
9] J. Bariwal, E. Van der Eycken, Chem. Soc. Rev. 2013, 42, 9283.
[
10] C. Sambiagio, S. P. Mersden, A. J. Blacker, P. C. McGovan, Chem.
Soc. Rev. 2014, 43, 3525.
[
11] V. A. Peshkov, O. Pereshivko, E. V. Van der Eycken, Chem. Soc.
Rev. 2012, 41, 3790.
[84,85]
nous catalytic systems described in Ref.
for the same
[12] G. Evano, N. Blanchard (Eds), Copper‐Mediated Cross‐Coupling
Reactions, 1st ed., John Wiley & Sons, Hoboken, NJ 2014.
3
A
coupling reaction. Furthermore, similarly to some
catalysts developed by other groups, catalyst 3‐Cu could
be used successfully several times.
[13] I. Goldberg, Ber. Dtsch. Chem. Ges. 1906, 39, 1691.
[14] A. S. Guram, R. A. Rennels, S. L. Buchwald, Angew. Chem. Int.
Ed. 1995, 34, 1348.
[15] J. P. Wolfe, S. Wagaw, J.‐F. Marcoux, S. L. Buchwald, Acc. Chem.
4
| CONCLUSIONS
Res. 1998, 31, 805.
[
[
[
[
[
[
[
16] D. S. Surry, S. L. Buchwald, Angew. Chem. Int. Ed. 2008, 47, 6338.
17] J. F. Hartwig, Angew. Chem. Int. Ed. 1998, 37, 2046.
18] J. F. Hartwig, Acc. Chem. Res. 2008, 41, 1534.
A series of the polymer supported Cu(II) amine and amine‐-
imine complexes based on the GMA gel and EDA or TAEA
and a series of salicylaldehydes were synthesized using
simple multi‐stage procedures. The complexes were
characterized using ICP‐OES, FTIR, DR UV–Vis, TGA
and SEM techniques and examined as catalysts in three types
coupling reactions. They were found rather as moderate
catalysts in the C‐N coupling reactions between imidazole
19] D. S. Surry, S. L. Buchwald, Chem. Sci. 2010, 1, 13.
20] J. C. Antilla, S. L. Buchwald, Org. Lett. 2001, 3, 2077.
21] T. D. Quach, R. A. Batey, Org. Lett. 2003, 5, 4397.
22] G. C. H. Chiang, T. Olsson, Org. Lett. 2004, 6, 3079.
[23] L. Rout, S. Jammi, T. Punniyamurthy, Org. Lett. 2007, 9, 3397.

1
4 of 15
BUKOWSKA ET AL.
[
24] M. L. Kantam, M. Roy, S. Roy, B. Sreedhar, R. L. De, Catal.
[53] K. R. Reddy, N. S. Kumar, B. Sreedhar, M. L. Kantam, J. Mol.
Catal. A: Chemical 2006, 252, 136.
Commun. 2008, 9, 2226.
[25] S. Sueki, Y. Kuninobu, Org. Lett. 2013, 15, 1544.
[54] C. Bodhak, A. Kundu, A. Pramanik, Tetrahedron Lett. 2015,
5
6, 419.
[26] A. R. Hajipour, F. Dordahan, F. Rafiee, M. Mahdavi, Appl.
Organomet. Chem. 2014, 28, 809.
[55] B. Yang, Z. Mao, X. Zhu, Y. Wan, Catal. Commun. 2015, 60, 92.
[
27] R. Mostafalu, B. Kaboudin, F. Kazemi, T. Yokomatsu, RSC Adv.
[56] M. Nasrollahzadeh, A. Zahraei, E. Pourbasheer, Monatsh. Chem.
2015, 146, 1329.
2
014, 4, 49273.
[28] N. Debreczeni, A. Fodor, Z. Hell, Catal. Lett. 2014, 144, 1547.
[57] A. M. Munshi, V. Agarwal, D. Ho, C. L. Raston, M. Saunders,
N. M. Smith, Cryst. Growth Des. 2016, 16, 4773.
[29] D. M. T. Chan, K. L. Monaco, R.‐P. Wang, M. P. Winters,
Tetrahedron Lett. 1998, 39, 2933.
[58] M. Abdollahi‐Alibeik, A. Moaddeli, RSC Adv. 2014, 4, 39759.
[
[
[
30] J. C. Antilla, J. M. Baskin, T. E. Barder, S. L. Buchwald, J. Org.
Chem. 2004, 69, 5578.
[59] B. J. Borah, S. J. Borah, L. Saikia, D. K. Dutta, Catal. Sci. Technol.
2014, 4, 1047.
31] S.‐Y. Moon, U. B. Kim, D.‐B. Sung, W.‐S. Kim, J. Org. Chem.
[60] H. Naeimi, M. Moradian, Appl. Catal. A: General 2013, 467, 400.
2
014, 80, 1856.
[
[
61] S. Yan, S. Pan, T. Osako, Y. Uozumi, Synlett 2016, 27, 1232.
32] M. Nasrollahzadeh, A. Rostami‐Vartooni, A. Ehsani, M.
Moghadam, J. Mol. Catal. A: Chemical 2014, 387, 123.
62] M. Islam, S. Mondal, P. Mondal, A. S. Roy, K. Tuhina, N. Salam, S.
Paul, D. Hossain, M. Mobarok, Transition Met. Chem. 2011,
36, 447.
[
[
33] J. Collman, M. Zhong, Org. Lett. 2000, 2, 1233.
34] P. Y. S. Lam, G. Vincent, C. G. Clark, S. Deudon, P. K. Jadhav,
[
[
63] S. M. Islam, N. Salam, P. Mondal, A. S. Roy, K. Ghosh, K. Tuhina,
Tetrahedron Lett. 2001, 42, 3414.
J. Molec. Catal. A: Chemical 2014, 387, 7.
[
[
[
[
[
[
35] J. C. Antilla, A. Klapars, S. L. Buchwald, J. Am. Chem. Soc. 2002,
64] B. Kodicherla, P. C. Perumgani, M. R. Mandapati, Appl.
Organometal. Chem. 2014, 28, 756.
1
24, 11684.
36] B. Mallesham, B. M. Rajesh, P. R. Reddy, D. Srinivas, S. Trehan,
[
[
65] M. M. Islam, A. S. Roy, S. M. Islam, Catal. Lett. 2016, 146, 1128.
66] A. Bukowska, W. Bukowski, J. Noworól, J. Appl. Polym. Sci. 2007,
Org. Lett. 2003, 5, 963.
37] H.‐J. Cristau, P. P. Cellier, J.‐F. Spindler, M. Taillefer, Eur. J. Org.
Chem. 2004, 695.
1
06, 3800.
[
[
67] A. Bukowska, W. Bukowski, J. Appl. Polym. Sci. 2012, 124(2), 904.
38] L. Yu, M. Wang, P. Li, L. Wang, Appl. Organomet. Chem. 2012,
68] E. Pretsch, P. Bühlmann, M. Badertscher, Structure Determination
of Organic Compounds. Tables of Spectral Data, 4th ed., Springer‐
Verlag, Berlin Heidelberg 2009.
2
6, 576.
39] S. M. Islam, S. Mondal, P. Mondal, A. S. Roy, K. Tuhina, N.
Salam, M. J. Mobarak, J. Organometal. Chem. 2012, 696, 4264.
[
[
[
69] Y.‐Z. Huang, H. Miao, Q.‐H. Zhang, C. Chen, J. Xu, Catal. Lett.
40] K. Inamoto, K. Nozawa, J. Kadokawa, Y. Kondo, Tetrahedron
2
008, 122, 344.
70] M. L. Kantam, B. P. C. Rao, B. M. Choudary, R. S. Reddy, Synlett
006, 14, 2195.
2
012, 68, 7794.
[
[
[
41] J. Li, S. Bénard, L. Neuville, J. Zhu, Org. Lett. 2012, 14, 5980.
2
42] R. A. Bohmann, C. Bolm, Org. Lett. 2013, 15, 4277.
71] M. B. Trost, C.‐J. Li, Modern Alkyne Chemistry: Catalytic and
atom‐economic transformations, Wiley‐VCH 2015.
43] S. Y. Moon, J. Nam, K. Rathwell, W.‐S. Kim, Org. Lett. 2014,
1
6, 338.
[
[
72] K. S. Sindhu, G. Anilkumar, RSC Adv. 2014, 4, 27867.
[
[
44] W.‐J. Yoo, L. Zhao, C.‐J. Li, Aldrichimica Acta 2011, 44, 43.
73] A. Fodor, Á. Kiss, N. Debreczeni, Z. Hell, I. Gresits, Org. Biomol.
Chem. 2010, 8, 4575.
45] A. Kochman, J. Skolimowski, L. Gebicka, D. Metodiewa, Pol. J.
Pharmacol. 2003, 55, 389.
[
[
[
[
74] G. Bosica, J. Gabarretta, RSC Adv. 2015, 5, 46074.
[
46] A. A. Boulton, B. A. Davis, D. A. Durden, L. E. Dyck, A. V.
75] R. Chinchilla, C. Nájera, Chem. Soc. Rev. 2011, 40, 5084.
76] C. D. Hein, X.‐M. Liu, D. Wang, Pharm. Res. 2008, 25, 2216.
77] X. Liu, B. Lin, Z. Zhang, H. Lei, Y. Li, RSC Adv. 2016, 6,
Juorio, X.‐M. Li, I. A. Paterson, P. H. Yu, Drug Develop. Res.
1
997, 42, 150.
47] C. Swithenbank, P. J. McNulty, K. L. Viste, J. Agric. Food Chem.
971, 19, 417.
[
[
[
9
4399.
1
[
78] S. Frindy, A. El Kadib, M. Lahcini, A. Primo, H. García, Catal. Sci.
Technol. 2016, 6, 4306.
48] M. L. Kantam, G. T. Venkanna, C. S. Sridhar, B. Sreedhar, B. M.
Choudrary, J. Org Chem. 2006, 71, 9522.
[79] P. Li, L. Wang, Tetrahedron 2007, 63, 5455.
49] P. R. Likhar, S. Roy, M. Roy, M. L. Kantam, R. L. De, J. Mol.
Catal. A: Chemical 2007, 271, 57.
[80] M. Wang, P. Li, L. Wang, Eur. J. Org. Chem. 2008, 2255.
[
[
50] R. B. N. Baig, R. S. Varma, RSC Adv. 2014, 4, 6568.
[81] B. Sreedhar, P. S. Reddy, C. S. V. Krishna, P. V. Babu, Tetrahedron
Lett. 2007, 48, 7882.
51] B. Kodicherla, C. P. Perumgani, M. R. Mandapati, Appl. Catal A:
General 2014, 483, 110.
[82] M. K. Patil, M. Keller, B. M. Reddy, P. Pale, J. Sommer, Eur. J.
Org. Chem. 2008, 4440.
[52] R. Arundhathi, D. C. Kumar, B. Sreedhar, Europ. J. Org. Chem.
2
010, 3621.
[83] H. Naeimi, M. Moradian, Appl. Organometal. Chem. 2013, 27, 300.

BUKOWSKA ET AL.
15 of 15
[
[
84] H.‐B. Chen, Y. Zhao, Y. Liao, RSC Adv. 2015, 5, 37737.
How to cite this article: Bukowska A, Bukowski W,
85] M. Varyani, P. K. Khatri, S. L. Jain, Catal. Commun. 2016, 77, 113.
Bester K, Hus K. Polymer supported copper(II) amine‐
3
imine complexes in the C‐N and A coupling
reactions. Appl Organometal Chem. 2017;e3847.
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