Synthesis and Characterization of Copper(I)‐Cysteine Complex Supported on Magnetic Layered Double Hydroxide as an Efficient and Recyclable Catalyst System for Click Chemistry Using Choline Azide as Reagent and Reaction Medium

Article abstract of DOI:10.1007/s10562-019-03011-2

Abstract: In this study, Fe₃O₄@LDH@cysteine–Cu(I) nanoparticles as a novel and recyclable catalytic system was designed and successfully synthesized. These nanoparticles show high catalytic activity for preparation of the triazole fa

Full text of DOI:10.1007/s10562-019-03011-2

Catalysis Letters
https://doi.org/10.1007/s10562-019-03011-2
Synthesis and Characterization of Copper(I)‐Cysteine Complex
Supported on Magnetic Layered Double Hydroxide as an Eꢀcient
and Recyclable Catalyst System for Click Chemistry Using Choline
Azide as Reagent and Reaction Medium
1
1
1
1
Farzane Pazoki · Arefe Salamatmanesh · Sepideh Bagheri · Akbar Heydari
Received: 6 June 2019 / Accepted: 27 October 2019
©
Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
In this study, Fe O @LDH@cysteine–Cu(I) nanoparticles as a novel and recyclable catalytic system was designed and suc-
3
4
cessfully synthesized. These nanoparticles show high catalytic activity for preparation of the triazole family through reaction
of the organic halides with alkynes in the presence of choline azide as reagent and reaction medium. In addition, Fe O @
3
4
LDH@cysteine–Cu(I) could be easily recovered and reused for ꢀve times without any signiꢀcant loss in catalytic activity.
Graphic Abstract
Keywords Layered double hydroxide · Choline azide · Click chemistry · Magnetic catalyst · Triazole
1
Introduction
Click chemistry is a powerful method for the synthesis
of substituted triazoles that has attracted enormous atten-
tion in modern chemistry. The term click chemistry was
proposed ꢀrstly by Sharpless and co-workers in 2001 [1]
that has many attractive features including high yielding,
simple to perform, excellent functional-group tolerance,
wide in scope, fast and highly eꢁcient reactions [2, 3].
Among click reactions, the Huisgen [3 + 2]-cycloaddition
of organic azides and alkynes by using copper(I) catalyst
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-019-03011-2) contains
supplementary material, which is available to authorized users.
*
Akbar Heydari
heydar_a@modares.ac.ir
1
Department of Chemical, Faculty of Sciences,
Tarbiat Modares University, PO Box 14155-4838,
1
4117-13116 Tehran, Iran
Vol.:(0
1
123456789)
3

F. Pazoki et al.
is one of the most important click reaction due to its high
regioselectivity and yield [4]. Also, 1,2,3-triazole deriva-
tives have shown a wide range of biological activity, such
as anticancer [5], anti-allergic [6], antiviral [7], anti-
bacterial [8], antidiabetic [9], anti-HIV activity [10] and
antimicrobial [11].
choline azide instead of using sodium azide and solvent in
this method.
2 Experimental
The copper(I)-catalyzed azide-alkyne cycloaddition
2.1 Materials and Instrumentation
(
CuAAC) could be studied by new conditions for the syn-
thesis of triazole. Various catalytic systems have been
employed for synthesis of triazoles, such as hydroxyapatite
All starting materials and solvents were purchased from
Merck Company and Sigma–Aldrich and Merck Company.
The monitoring of reaction progress was performed by ana-
lytical thin layer chromatography (TLC) on Merck 0.2 mm
of silica gel 60F-254 Al-plates.
[
12] polysaccharide-supported nanoparticles [13], polyden-
tate [14], CuO–HMSS [15], zeolite [16] [MNPs@FGly][Cl]
[17], however there is still a requirement for the development
1
of new eꢁcient, widely applicable, usage of cheap and low
toxicity reagent, feasible as well as eco-friendly method for
synthesis of 1,2,3-triazoles.
All structure of compounds were identiꢀed. H NMR
(500 MHz) spectra was determined on Bruker DRX-500
Advance spectrometers with CDCl as solvent at ambient
3
Recent examples include the use of sodium azide as
the source of azide in click reaction which this material is
acutely toxic [18] and needs using solvent. The sources of
azide can be choline azide that is used as an ionic liquid
and azidation reagent. Ionic liquids have attracted signiꢀ-
cant attention due to the use as green solvent and catalyst
for chemistry process. Choline azide is prepared by choline
chloride and sodium azide, which can be used as a “green”
solvent and safe azidation reagent for the synthesis of sub-
stituted triazoles in both laboratories and industrial applica-
tions [19].
temperature by using TMS as the internal standard. Fourier
transform infrared spectroscopy (FT-IR) was obtained on
a Shimadzu FT-IR-8400S spectrometer by using the KBr
plate technique.
Energy-Dispersive X-ray spectroscopy (EDX) spectra
was performed by an Oxford Instrumental and also Field
Emission Scanning Electron Microscopy (FE-SEM) image
was obtained on Zeiss-Sigma VP 500. The magnetic meas-
urements experiments were performed by using a vibrating
magnetometer/alternating gradient force magnetometer (MD
Co., Iran, www.mdk-magnetic.com). Transmission electron
microscopy (TEM) was obtained at 120 kV (Philips, model
CM120). X-ray diꢂraction pattern (XRD) was recorded by
a Philips X-Pert 1710 diꢂractometer.
Several heterogeneous and homogeneous copper-based
catalytic systems were studied on CuAAC reactions [20–24],
Among a new generation of heterogeneous catalysts, layered
double hydroxides (LDHs) coated magnetite nanoparticles
are indeed an eꢂective surface of modiꢀed magnetic nan-
oparticle (MNP) which has low toxicity, facile synthesis,
moisture, and air stability [25–29]. The resulting LDHs can
be readily modiꢀed with cysteine through covalent bonding.
LDHs are introduced by the general formula [M II M III
2.2 Preparation of Fe O
3
4
Generally, Fe O was prepared by coprecipitation method.
3
4
The FeCl .6H O (10 mmol) and FeCl .4H O (5 mmol)
3
2
2
2
were dissolved in water (120 ml) under vigorous stirring
1
–x
x
x+
n–
(
OH) ] (A ) ·yH O, that M(II) and M(III) cations occu-
(800 rpm). Then, NH OH (10 ml) was added dropwise to
2
x/n
2
4
n−
pied octahedral holes in a brucite-like layer and A anion
produce a black solid product (pH about 11) and then the
mixture was reꢃuxed for 1 h under argon. Finally, the black
nanoparticles were separated by an external magnet from the
aqueous solution, then washed with deionized water several
times until the solution was neutral, and dried in an oven at
50 °C for 24 h.
2
+
is present in the hydrated interlayer. The molar ratio of M /
2
+
3+
(
M +M ) is equal to the amount of x [30].
In continuation of our eꢂorts in the development of sim-
ple and eꢁcient protocols for synthesis of triazoles [31],
herein, we report copper(I)-cysteine complex immobi-
lized on the surface of LDH coated magnetite nanoparti-
cles, Fe O @LDH@cysteine–Cu(I), as an efficient and
2.3 Preparation of Fe O @LDH
3
4
3 4
recoverable nanocatalyst for the synthesis of a number of
1
,2,3-triazoles. The magnetic catalyst is easily separated by
The Fe O @LDH was prepared by dispersing about 1.0 g of
3 4
an external magnet and has several beneꢀts such as thermal
stability, recoverability and high surface. In this work, we
observed remarkable catalytic activity of Fe O @LDH@
Fe O in 50 mL of water and 50 mL of methanol for 15 min.
3 4
Then, 30 mL solution of NaOH (0.8 M) was added dropwise
to reach pH 12. And then the mixture of Mg(NO ) .6H O
3
4
3 2
2
cysteine–Cu(I) nanocatalyst in click Chemistry of organic
halide derivatives, choline azide and alkynes. Therefore, this
method is a green and eꢂective rout because of employing
(9 mmol) and Al(NO ) .9H O (3 mmol) in 100 mL H O
3 3 2 2
(Mg/Al = 3/1) was added dropwise to the above suspen-
sion to reach pH=10. After that, the temperature raised to
1
3

Synthesis and Characterization of Copper(I)‐Cysteine Complex Supported on Magnetic Layered…
6
0 °C for 24 h. Then the resulting product was separated by
2.6 Catalytic Click Reaction in Presence of Fe O @
3 4
an external magnet and thoroughly washed with deionized
water and ethanol until the solution was neutral, and dried
in an oven at 50 °C for 24 h.
LDH@cysteine‑Cu(I)
A mixture of alkyl halide (2 mmol), terminal alkyne
2 mmol) and choline azide (3 mmol) was stirred at 75 °C in
(
the presence of 20 mg Fe O @LDH@cysteine-Cu(I) nano-
3
4
2
.4 Preparation of Fe O @LDH@Cysteine–Cu(I)
catalyst. After completion of the reaction, the product was
decanted by dilution of the residue with water and separated
the magnetic catalyst by an external magnet and the solid
3
4
The Fe O @LDH@cysteine was prepared by dispersing
3
4
about 1.0 g of Fe O @LDH in 50 mL of water. Then, NaOH
product was puriꢀed by recrystallization from EtOH: H O
3
4
2
(
0.8 M) was added dropwise to reach pH about 11. After that
(2:1 v/v). In some cases, products have to be isolated using
1
.5 mmol cysteine was added to this suspension. This solu-
chromatography on silica gel.
tion was reꢃuxed for 24 h. Next, the resulting product was
separated by an external magnet and thoroughly washed with
deionized water and ethanol until the solution was neutral,
and dried in an oven at 50 °C.
3 Results and Discussions
1
g of Fe O @LDH@cysteine was dispersed in
The method for the preparation of Fe O @LDH@
3
4
3
4
THF (50 mL) in an ultrasonic bath for 10 min, then CuI
Cysteine–Cu(I) is depicted in Scheme 1. Fe O was synthe-
3 4
(
0.5 mmol) was dispersed in dry THF (15 mL) after stirred
sized by co-precipitation process. Next, Fe O @LDH pre-
3 4
at room temperature for 24 h. Finally, the product was sepa-
rated by an external magnet and dried in an oven at 50 °C
for 24 h (Scheme 1).
pared with Mg(NO ) .6H O and Al(NO ) .9H O in presence
3 2 2 3 3 2
NaOH. In the following, reaction of cysteine with magnetic
layered double hydroxide led to produce Fe O @LDH@
3
4
Cysteine. Finally, Copper(I)-cysteine complex supported on
magnetic layered double hydroxide nanoparticles were syn-
thesized by treatment of CuI with Fe O @LDH@Cysteine
2
.5 Preparation Choline Azide
3
4
for 24 h. Characterization of the catalyst was performed by
using diꢂerent techniques for example FT-IR, FE-SEM,
TEM, EDX, TGA, XRD and vibrating sample magnetom-
etry (VSM). FT-IR of Fe O (Blue curve), Fe O coated with
A mixture of choline chloride (10 mmol), Sodium azide
10 mmol) and methanol (50 ml) was stirred at 65 °C for 6 h.
After completion of the reaction, the product separated by
ltered oꢂ and solvent of solution evaporate under reduced
pressure and choline azide was separated as oily residue
19].
(
3
4
3
4
ꢀ
LDH (Orange curve), Fe O @LDH@cysteine (Grey curve)
3 4
and Fe O @LDH@cysteine–Cu(I) before (Black curve)
3
4
[
and after reaction (Green curve) were depicted in Fig. 1.
−
1
The band Fe–O stretching vibration appeared at 578 cm .
−
1
The O–H stretch of Fe O @LDH (3440 cm ) was stronger
3
4
than that of Fe O @LDH@cystein-Cu(I) due to cysteine
3
4
interacts with the LDH and weakens the O–H vibration. As
Fig. 1 The FT-IR spectra of the Fe O (Blue curve), Fe O @LDH
3
4
3
4
(
Orange curve), Fe O @LDH@cysteine (Grey curve) and Fe O @
3 4 3 4
Scheme 1 Preparation of Fe O @LDH@Cysteine–Cu(I) nanocata-
LDH@cysteine-Cu(I) before (Black curve) and after reaction (Green
curve)
3
4
lyst
1
3

F. Pazoki et al.
(
422), (511) and (440) lattice planes respectively. These
XRD peaks conꢀrm well to Fe O , which are in agreement
3
4
with work done by Wei et al. [32]. This fact observes which
the structure of Fe O nanoparticles is kept after the surface
3
4
modiꢀcation with LDH@cysteine–Cu(I). Additional diꢂrac-
tion peaks at around 13.23°, 26.79°, and 40.73° are related
to Mg–Al LDH [33]. These results indicate that Fe O @
3
4
LDH@cysteine–Cu(I) have been successfully synthesized.
The intercalated cysteine -LDH appeared a few shift of the
(
003), (006) and (440) reꢃections to lower angles, which
agreed with intercalation cysteine into the inter-layer of the
layered double hydroxide. The basal spacing’s of the Lay-
ered double hydroxide could be calculated from the basal
reꢃection by using Bragg’s equation, λ = 2dsinθ. λ is the
wavelength of Cu-Kα radiation, and θ is the half of the scat-
tering angle of (0 0 3) peak. Results indicated that the inter-
layer spacing of Fe O @LDH@cysteine–Cu(I) (Å) is larger
Fig. 2 Magnetization curves of Fe O (Blue curve) and Fe O @
3
4
3
4
LDH@ cysteine-Cu(I) (Black curve)
3
4
than that of Fe O @LDH (Å), demonstrating the intercala-
3
4
tion of Fe O @LDH by a little of amount cysteine [34].
3
4
EDX analysis was used to give information about the
elements present in Fe O @LDH@cysteine-Cu(I) (Fig. 4).
3
4
EDX pattern clearly conꢀrms the good dispersion of mag-
netic solid. Chemical characterization of the typical sam-
ple shows the presence of iron (34.36 wt%), magnesium
(
7.57 wt%), aluminium (1.07 wt%), nitrogen (1.17 wt%),
sulphur (0.09 wt%), carbon (6.39 wt%), oxygen (47.46 wt%)
and copper (1.88 wt%).
The size and the morphology of Fe O @LDH@cysteine-
3
4
Fig. 3 The X-ray diꢂraction patterns of Fe O @LDH@cysteine-
Cu(I) were investigated by using Fe-SEM and TEM that the
3
4
Cu(I) (Black) and Fe O @LDH (Orange)
3
4
Fe O @LDH@cysteine-Cu(I) nanoparticles were orderly
3
4
decorated with spherical particles with particles size of
can be seen in Fig. 1, the major peaks appeared at 3440-
about 27 to 30 nm (Fig. 5).
−
1
−1
3
471 cm (hydroxyl O─H), 1388-1403 cm (Fe–O stretch-
Quantitative determination of the cysteine loaded on the
surface of Fe O @LDH was performed utilizing Thermo-
ing). Vibration in the FT-IR spectra of Fe O @LDH@
3
4
3
4
−
1
cysteine at 1583 cm with Fe O @LDH@cystein–Cu(I) at
gravimetric analysis (TGA) (Fig. 6). The TGA pattern of
3
4
−
1
1
612 cm prove formation of the complex. Also, it shows
the nanocatalyst was recorded at a rate of 20 °C/min within
that the Fe O @LDH@cystein-Cu(I) nanoparticles have
the range of 20–800 °C under the N atmosphere. The ꢀrst
3
4
2
the same structure after 5 cycles (Green curve) and this the
weight loss appeared below 200 °C that is probably related
to evaporation of adsorbed moisture. This is followed by a
second peak at rang 170 °C and 428.93 °C, corresponding
to the decomposition of the cysteine complex (weight loss of
about 21.68%), Furthermore, according to thermal analysis,
the nanoparticle was stable up to 170 °C.
structure is stable.
The magnetic possession of the Fe O (Blue curve) and
3
4
Fe O @LDH@cysteine–Cu(I) (Black curve) was investi-
3
4
gated by VSM (Fig. 2). Magnetic hysteresis measurements
were done in an applied magnetic ꢀeld with the the range
of − 10000 to + 10000 Oe. Nanoparticles of Fe O pos-
Triazole compounds are widely used in the pharma-
ceutical industry. This method was chosen to evaluate the
environmental eꢂect of safe azidation reagent and catalytic
activity. Choline azide is green reagent and safe solvent
which developing a clean and cheap method for synthesis
of triazole. Our preliminary experiments show that Fe O @
3
4
sessed high saturation magnetization 53 emu/g at 25 °C and
decreased to 32.35 emu/g for Fe O @LDH@cysteine–Cu(I).
3
4
The formation of Fe O @LDH@cysteine–Cu(I) takes place
3
4
simultaneously due to Fe O @LDH@cysteine–Cu(I) had
3
4
lower magnetization as compared with that of Fe O .
3
4
3
4
As can be seen in Fig. 3, these five peaks of the
LDH@cysteine-Cu(I) is a more eꢁcient promoter for the
Fe O could be seen for the synthesized Fe O @LDH@
rapid and convenient catalyst for click chemistry.
3
4
3
4
cysteine–Cu(I) (2θ=35.12°, 41.44°, 50.52°, 63°, 67°, and
The yields of triazole from the click chemistry with
benzyl bromide, propargyl alcohol and catalyst of Fe O @
7
4°). The ꢀve peaks correspond to the (220), (311), (400),
3
4
1
3

Synthesis and Characterization of Copper(I)‐Cysteine Complex Supported on Magnetic Layered…
Fig. 4 a EDX analysis of the
Fe O @LDH@cysteine-Cu(I)
3
4
NPs; b Weight percent of vari-
ous elements on the surface of
Fe O @LDH@cysteine-Cu(I)
3
4
NPs from EDX analysis
Fig. 5 a FE-SEM micrographs
of Fe O @LDH@cystein_Cu(I)
3
4
b TEM image
LDH@cysteine-Cu(I), (Scheme 2) with various solvent,
amount catalyst and temperature are summarized in Table 1
the reaction time is 35 min in water, higher than the reac-
tion time when choline azide was used as a solvent (25 min)
(Table 1, Entry 1 and 7). Finally, we used the 15, 20, 30, 40
and 50 mg of the catalyst in this reaction for indicating the
best amount of catalyst. (Table 1, Entry 4, 5, 6, 7 and 8). The
(
Entries 1–6).
The reaction proceeds slowly in acetonitrile and metha-
nol (Table 1, Entry 2 and 3). As can be seen in this table,
1
3

F. Pazoki et al.
Also, Fe O @LDH@cysteine–Cu(I) resulted in quantita-
3
4
tive yield better than Fe O @cysteine–Cu(I) due to more
3
4
active sites of LDH for linked to cysteine (Table 2, Entry
3
and 4).
The click reaction of choline azide with various alkynes
and aryl halides performed by using the optimized condi-
tions described above. Finally, the desired triazoles were
generated in good to excellent yields. (Table 3).
When Phenylacetylene with P-methoxy benzyl bromide
and benzyl bromide were used in the reaction, the cor-
responding product was obtained in the excellent yield
(
Table 3, Entry 1 and 2).
Allyl bromide or 2-bromo-4-nitroacetophenone with
choline azide and phenylacetylene aꢂorded the desired
triazole in the good yield (Table 3, Entry 8 and 11).
The last generally proposed mechanism of this reaction
is shown in Scheme 3 [35] Initially, formation of Cu(I)
complex was followed by reaction of two Cu(I) ions and
arylacetylene for some time, In the next step, alkyl azide
preparation in situ from choline azide and alkyl halide then
nitrogen of alkyl azide attack to Cu(I) complex. Finally,
Triazole was formed in choline azide by protonolysis.
In addition, the reusability of the Fe O @LDH@
Fig. 6 TGA of Fe O @LDH@cystein_Cu(I)
3
4
3
4
cysteine–Cu(I) catalyst was evaluated using benzyl bro-
Scheme 2 Fe O @LDH@cysteine–Cu(I) catalyzed click chemistry
3
4
mide, propargyl alcohol in choline azide as a model
Table 1 Optimization of the
reaction conditions of click
chemistry
Yield (%)c
Entry
Temperature (°C)
Amount cata- Solvent
lyst (g)
Time (minute)
1
2
3
4
5
6
7
8
Reꢃux
Reꢃux
Reꢃux
75
75
75
0.02
0.02
0.02
0.05
0.04
0.03
0.02
0.015
Watera
35
40
40
25
25
25
25
35
85
70
80
90
90
90
90
85
a
CH CN
3
a
CH OH
3
b
b
b
Choline azide
Choline azide
Choline azide
Choline azide
Choline azide
b
75
75
b
a
Reaction condition: Benzyl halide (2 mmol), Alkyne (2 mmol), Sodium azide (3 mmol), Fe O @LDH@
3
4
cysteine-Cu(I) (20 mg), 75 °C
b
Benzyl halide (2 mmol), Alkyne (2 mmol), Choline azide (3 mmol), diꢂerent amount of Fe O @LDH@
3
4
cysteine-Cu(I), 75 °C in diꢂerent solvent
c
Isolated yields
best result was performed by using 20 mg Fe O @LDH@
3
4
cysteine–Cu(I) at 75 °C in choline azide (Entry 7).
Table 2 Screening of the catalysts
The eꢁciency of the Fe O @LDH@cysteine–Cu(I),
3
4
Entry
Catalyst
Yield (%)
Fe O @cysteine–Cu(I) and CuI (5 mol%) were compared
3
4
1
2
3
4
None
<5%
99%
85%
90%
under identical conditions (Table 2). When the mixture
was heated to 75 °C without any catalyst no product was
observed (Table 2 Entry 1). This reaction was performed
by the homogeneous catalyst (CuI) that the resulting of
this reaction is excellent (Table 2 Entry 2) but the separa-
tion of this catalyst from mixture reaction was diꢁcult.
CuI (5 mol %)
Fe O @cysteine–Cu(I)
3
4
Fe O @LDH@cysteine–Cu(I)
3
4
Reaction condition: Benzyl halide (2 mmol), Alkyne (2 mmol), Cho-
line azide (3 mmol), 75 °C, various catalyst
1
3

Synthesis and Characterization of Copper(I)‐Cysteine Complex Supported on Magnetic Layered…
Table 3 Synthesis of 1,2,3-triazoles from organic halides, alkynes and choline azide using Fe O @LDH@cysteine–Cu(I)
3
4
Entry
1
Halide
Alkyne
Product
Yield (%)a
Br
N
N
O
N
97
O
Cl
Br
N
N
N
2
3
95-97
90
and
Br
N
N
Cl
Cl
N
Cl
Cl
Cl
N
N
N
4
5
95
90
NO
2
Br
N
OH
N
N
OH
O2N
Br
Br
N
N
6
96
N
Br
Br
NO
2
N
N
7
8
88
80
N
NO
2
N
N
N
Br
1
3

F. Pazoki et al.
Table 3 (continued)
Entry
Halide
Alkyne
Product
Yield (%)a
O
O
Br
N
N
N
9
87
85
O
Br
O
N
N
Cl
N
1
1
1
0
1
2
Cl
O
Br
O
N
N
NO
2
N
80
90
NO
2
Br
N
N
N
F
F
Br
N
N
OH
1
1
3
4
N
90
87
OH
Br
O
N
N
N
OH
O
OH
Br
OH
N
N
OH
1
5
6
N
82
94
Br
N
N
N
1
Reaction conditions: Benzyl/Alkyl halide (2 mmol), Alkyne (2 mmol), Choline azide (3 mmol), Fe O @LDH@cysteine-Cu(I) (20 mg), 75 °C
3
4
a
Isolated yields
reaction. After each run the nanoparticles were separated
by a permanent magnetic then washed with ethyl acetate,
air-dried and applied in the next run (Fig. 7). Surprisingly,
it is found that the magnetic nanoparticles were recovered
and reused for 5 runs without any signiꢀcant loss in the
eꢁciency of the catalyst.
The results obtained for the click reaction under the opti-
mized conditions were compared with previously reported
catalysts in the literature. It can be seen in Table 4 that the
1
3

Synthesis and Characterization of Copper(I)‐Cysteine Complex Supported on Magnetic Layered…
Scheme 3 Proposed mechanism
of click reaction
present catalyst showed a good catalytic activity. Notice-
ably, this new catalyst is comparable in terms of price, eco-
friendly, reusability, commercially available materials, easy
preparation and facile separation.
4
Conclusions
We have demonstrated for the ꢀrst time the use of cheap
and magnetic LDH as support for immobilizing Cu(I). The
catalytic activity of the Fe O @LDH@cysteine–Cu(I)
3
4
nanoparticles were studied for the click chemistry reaction.
The main advantage of this method employs safe and green
Fig. 7 Recyclability study of the catalyst in the preparation of
,2,3-triazoles
1
Table 4 Comparison of the catalytic eꢁciency of Fe O @LDH@cysteine–Cu(I) with the previously reported catalytic systems in the click reac-
3
4
tion
Entries Catalyst
Reaction conditions
Yield (%)
86 [36]
1
2
3
4
5
6
Cu NPs
Phenyl acetylene (0.5 mmol), benzyl chloride (0.6 mmol), NaN (0.6 mmol), CH OH
3
3
(
2 mL), r.t., 10 h
Fe O -DOPA-CuNPs
Phenyl acetylene (1 mmol), benzyl bromide (1.2 mmol), NaN (1.5 mmol), H O (5 ml),
96 [37]
93 [38]
3
4
3
2
1
20 °C, 10 min
HCP-NHC–Cu
CFL
Phenyl acetylene (1.0 mmol), benzyl chloride (1.0 mmol), NaN (1.1 mmol), EtOH
3
(
2.0 mL),80 °C, 8 h
Benzyl chloride (1.0 mmol), Phenyl acetylene (1.0 mmol), NaN (1.0 mmol) in EtOH: H O, 85 [39]
3
2
r.t, 1.5 h
Phenyl acetylene (1.0 mmol), benzyl chloride (1.0 mmol), NaN (1.3 mmol), H O (2.0 mL), 97 [40]
MNP@SPAAm/Cu
3
2
Na-ascorbate (10 mol%), 50 °C, 3 h
Fe O @LDH@cysteine–Cu(I) Benzyl halide (2 mmol), Alkyne (2 mmol), Choline azide (3 mmol), 75 °C, 25 min
95-97
3
4
1
3

F. Pazoki et al.
azidation reagent and using the magnetically separable and
recyclable catalyst. Also, The Fe O @LDH@cysteine–Cu(I)
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