Copper(II) Acetylacetonate: An Efficient Catalyst for Huisgen-Click Reaction for Synthesis of 1,2,3-Triazoles in Water

Article abstract of DOI:10.1002/cjoc.201700007

An efficient and green copper(II) acetylacetonate-catalyzed protocol for the Huisgen-click reaction in water at 100 °C has been established. The protocol was not only suitable for the reaction between organic azides and alkynes, but also suitable for one-pot three-component reaction among alkyl halides, NaN₃ and alkynes.

Full text of DOI:10.1002/cjoc.201700007

COMMUNICATION
DOI: 10.1002/cjoc.201700007
Copper(II) Acetylacetonate: An Efficient Catalyst for Huisgen-
Click Reaction for Synthesis of 1,2,3-Triazoles in Water
Yuqin Jiang,a Xingfeng Li,a Xiyong Li,b Yamin Sun,b Yaru Zhao,a Shuhong Jia,a
Niu Guo,a Guiqing Xu,*,a and Weiwei Zhang*,a
a Henan Engineering Laboratory of Chemical Pharmaceuticals & Biomedical Materials, Collaborative Innovation
Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media
and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University,
Xinxiang, Henan 453007, China
b Weihai Ocean Vocational College, Weihai, Shandong 264300, China
An efficient and green copper(II) acetylacetonate-catalyzed protocol for the Huisgen-click reaction in water at
100 ℃ has been established. The protocol was not only suitable for the reaction between organic azides and al-
kynes, but also suitable for one-pot three-component reaction among alkyl halides, NaN3 and alkynes.
Keywords copper(II) acetylacetonate, Huisgen-click reaction, water, alkynes , one-pot
Introduction
The Huisgen-click reactions have been successfully car-
ried out in green solvents, such as scCO2,[26] ionic liq-
uids,[27] water[28] and so on. Therefore, water is still the
preferred benign and suitable solvent for the Huisgen-
click reaction.
1,4-Disubstituted 1,2,3-triazoles are important
N-heterocyclic compounds, which have also been
widely applied in industrial applications such as materi-
al science,[1] polymer chemistry,[2] pharmaceutical syn-
thesis[3] and biological conjugation.[4] In addition,
1,2,3-triazoles are important privileged scaffolds and
basic skeletons with a broad spectrum of biological ac-
tivities, such as anti-tumour,[5] anti-viral,[6] antiallergic,[7]
fungicidal,[7b] anti-HIV[8] activities and so on. The clas-
sical method for synthesis of 1,2,3-triazoles is the ther-
mal Huisgen reaction between the terminal alkynes and
azides, which has been considered as one of the im-
portant reactions for synthesis of five-member nitrogen
heterocycles in organic chemistry.[9-11]
Since the Huisgen-click reaction catalyzed by cop-
per(I) species for regioselective synthesis of 1,4-disub-
stituted 1,2,3-triazoles was independently discovered by
the groups of Sharpless[12] and Meldal,[13] a kind of
copper catalytic systems were developed for the Huis-
gen-click reaction, including copper(I) salts and their
complexes,[14] copper(II) salt using appropriate reducing
agents[12,15,16] and metallic copper.[17] Considering the
instability of simple copper(I) species, Cu(II) species
were also applied for the Huisgen-click reaction, such as
copper(II) complexes,[18] nanocrystalline copper ox-
ide(II),[19] copper(II) on supports.[20-24] In addition, be-
nign solvents are also the crucial factor for environ-
mentally and friendly sustainable chemical processes.[25]
Copper(II) acetylacetonate [Cu(acac)2] complexes
have been widely used in organic chemistry as efficient
catalysts for C－X (X＝C, N, P) bond formation,[29]
asymmetric sulfoxidation,[30] C－H or C－C cleav-
age,[31] synthesis of (E)-β-chloro-enesulfonamides,[32]
substituted ketones[33] and sulfur-containing triazoles.[34]
In most cases mentioned above, Cu(acac)2 was used as a
homogeneous catalytic system. For a recyclable proto-
col, efforts were put to make Cu(acac)2 as an heteroge-
neous recyclable catalytic system by immobilizing on
supports, such as active carbon,[35] mesoporous silica,[36]
caly,[37] ionic liquids,[38] core-shell structured
[39]
Fe3O4@SiO2 and so on. It is worthy mentioning that
Cu(acac)2 has poor solubility in water, which is the pre-
ferred green solvent for organic transformation and
would make Cu(acac)2 act as heterogeneous catalysts.
To the best of our knowledge, Cu(acac)2 has not been
used lonely as the catalyst for the Huisgn-click reaction
in water. In continuation with our previous works on the
Cu(II) species-catalyzed Huisgen-click reaction,[26c,28j]
the main work described in this paper shows a green and
efficient protocol using Cu(acac)2 as the catalyst for
Huisgen-click reaction in water at 100 ℃ without any
bases or ligands at a relatively low catalyst loading (0.2
mol%).
*
E-mail: zhangweiwei@htu.edu.cn; Tel.: 0086-0373-3326335; Fax: 0086-0373-3326335
Received January 10, 2017; accepted February 22, 2017; published online XXXX, 2017.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201700007 or from the author.
Chin. J. Chem. 2017, XX, 1—7
© 2017 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

Jiang et al.
COMMUNICATION
Experimental
General procedure for cycloaddition reaction be-
tween alkynes and azides
Alkyne (1.0 mmol), azide (1.0 mmol), and copper(II)
acetylacetonate (0.002 mmol) were dissolved (or sus-
pended) in deionized water (2.0 mL). The mixture was
reacted at 100 ℃ and monitored by TLC until the
starting materials disappeared. After the completion of
the reaction, the resulting solution was extracted with
ethyl acetate. The organic phase was dried with anhy-
drous Na2SO4, and the solvent was removed to give the
corresponding triazoles, which were purified by column
chromatography (petroleum ether/ethyl acetate, V∶V＝
6∶1).
Figure 1 Effects of reaction temperature on the model reaction.
as the temperature for the model reaction.
General procedure for one-pot three-component
1,3-dipolar cycloaddition catalyzed by copper(II)
acetylacetonate in water
To investigate the influence of the catalyst loading
on the cycloaddition, the model reaction was performed
at 50 ℃ catalyzed by different amounts of Cu(acac)2.
As shown in Table 1 (Entries 1, 2), the model reaction
could still finish in 30 min, when catalyzed by 10 mol%
or 5 mol% Cu(acac)2 with almost the same yields as that
when catalyzed by 20 mol% Cu(acac)2. However, a fur-
ther decrease of the loading of Cu(acac)2 (Entries 3－6)
led to a long reaction time. The reaction time was 120
min when catalyzed by 2 mol% Cu(acac)2, which was
four times that when catalyzed by 5 mol% Cu(acac)2.
When catalyzed by 1 mol%, 0.5 mol%, and 0.2 mol%
Cu(acac)2, the corresponding reaction time was 240,
270 and 360 min, respectively. It is worthy mentioning
that although the longest reaction time was taken when
catalyzed by 0.2 mol% Cu(acac)2, it was the enough
catalyst loading for completing the model reaction. Ac-
cording to our previous works on the Cu(II) catalyzed
Huisgen-click reaction,[28j] elevating the reaction tem-
perature is a direct way to short reaction time. To im-
prove the efficiency of 0.2 mol% Cu(acac)2 on the mod-
el reaction, the reaction temperature was increased to 80
and 100 ℃. It is uplifting that the reaction time was 90
min for 80 ℃ (Entry 7) and 50 min for 100 ℃ (Entry
8). Therefore, the optimized conditions are as follows:
Cu(acac)2 (0.2 mol%) as the catalyst, water (2.0 mL) as
the solvent, and 100 ℃ as the reaction temperature.
Alkyne (1.0 mmol), sodium azide (1.2 mmol), alkyl
halide (1.0 mmol), and copper(II) acetylacetonate (0.02
mmol) were dissolved (or suspended) in deionized wa-
ter (2.0 mL). The mixture reacted at 100 ℃ and was
monitored by TLC until the starting materials
disappeared. After the completion of the reaction, the
resulting solution was extracted with ethyl acetate. The
organic phase was dried with anhydrous Na2SO4, and
the solvent was removed to give the corresponding tria-
zoles, which were purified by column chromatography
(petroleum ether/ethyl acetate, V∶V＝6∶1).
Results and Discussion
Our investigation began with an effort to optimize
the reaction temperature for the model reaction using
phenyl azide and propargyl phenyl ether as the starting
materials (Eq. 1). The reaction conditions were settled
as follows: phenyl azide (1.0 mmol), propargyl phenyl
ether (1.0 mmol), Cu(acac)2 (20 mol%) and water (2.0
mL). The model reaction was carried out at 25, 40, 50,
80 and 100 ℃ for 30 min. As shown in Figure 1, the
obtained yields of the model reaction increased greatly
with the temperature range from 25 to 50 ℃ and kept
almost the same with the temperature range from 50 to
100 ℃. The obtained yields of the model reaction at 25
and 40 ℃ were only 5% and 40% respectively. While
at 50 ℃, the obtained yield of the model reaction was
91%, which indicated that the reaction temperature has
a great effect on the model reaction. And elevating the
reaction temperature to 80 or 100 ℃, the obtained
yields of the model reaction were almost the same as
that obtained at 50 ℃. Therefore, 50 ℃ was selected
Table 1 Effects of catalyst loading on the model reaction
Entry Catalyst loading/mol% Temp./℃ Time/min Yield/%
1
2
3
4
5
6
7
8
10
5
50
50
50
50
50
50
80
100
30
30
94
93
92
91
92
91
93
92
2
120
240
270
360
90
1
0.5
0.2
0.2
0.2
50
2
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Chin. J. Chem. 2017, XX, 1—7

Catalyst for Synthesis of 1,2,3-Triazoles in Water
With the optimized reaction conditions established,
the scope of this reaction was then evaluated with re-
spect to various substituted terminal alkynes and azides.
As shown in Table 2, these transformations displayed
high functional group tolerance and proved to be a gen-
eral method for the synthesis of 1,4-disubstituted
1,2,3-triazoles. Terminal alkynes with ethyl, ethoxyl and
amino groups on the arene or aliphatic alkynes gave the
corresponding 1,2,3-triazoles in good to excellent yields.
And the reactions worked well not only with aryl azides,
but also with alkyl azides. It was also found that the
substituents (electron withdrawing, electron rich and
heterocycle) do not have any peculiar effects, as most of
the reactions were completed within 20－200 min.
However, aliphatic azide (ethyl 2-azidoacetate) and ali-
phatic alkyne (1-octyne) took a relatively longer reac-
tion time for the formation of triazoles (Table 2, Entry 8
and Entry 21).
Table 2 Synthesis of triazoles using Cu(acac)2 as the catalysta
N
R1
N
copper(II) acetylacetonate (0.2 mol%)
H2O, 100 oC
N
R2
R1 N3
+
R2
Entry
1
Azide
Alkyne
Product
Time/min
50
Yieldb/%
93
O
O
O
N
N
N
N
N
N
O
O
2
3
90
75
89
91
O
N3
O
O
4
5
100
120
80
84
86
84
90
83
90
89
F
O
N
N
N
N3
6
O2N
O2N
N3
O
O
O
7
50
8
180
30
9
10
20
Chin. J. Chem. 2017, XX, 1—7
© 2017 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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3

Jiang et al.
COMMUNICATION
Continued
Yieldb/%
Entry
11
Azide
Alkyne
Product
Time/min
30
93
88
90
89
87
NH2
O
12
13
14
15
60
90
40
60
N
N
N
N
N
N
N3
O2N
16
17
18
19
20
120
90
83
85
83
82
82
NH2
N
N
N
OH
100
120
130
N
N
N
O
200
84
21
a Reaction conditions: terminal alkyne (1.0 mmol), azide (1.0 mmol), Cu(acac)2 (0.2 mol%), H2O (2 mL), 100 ℃. b Isolated yields.
Furthermore, we have also developed an experimen-
tally convenient one-pot, regioselective protocol for
synthesis of 1,2,3-triazoles from alkyl halides, NaN3,
and alkynes. It is worthy mentioning that the catalyst
loading needed for three-component ont-pot reaction is
2 mol%. Therefore the optimized conditions are as fol-
lows: terminal alkyne (1.0 mmol), sodium azide (1.2
mmol), alkyl halide (1.0 mmol), Cu(acac)2 (2 mol%),
H2O (2.0 mL) and 100 ℃. As shown in Table 3, the
corresponding 1,4-disubstituded 1,2,3-triazoles could be
obtained in good to excellent yields under such condi-
tions.
gen-click reaction has been proposed according to the
previous reports.[19,23,28n,28j] As for reaction between the
azides and alkynes, it seems that the Cu(II) has been
reduced by alkynes to Cu(I),[28n] which is the true cata-
lyst. As for three-component 1,3-dipolar cycloaddition,
copper(II) acetylacetonate might be reduced by sodium
azide to give the needed catalysis of Cu(I).[23,28j]
Conclusions
In summary, we presented a simple protocol for the
Huisgen click reaction using Cu(acac)2 as the catalyst in
water at 100 ℃. The protocol was also proved to be
The catalytic mechanism of copper(II) for Huis-
4
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Chin. J. Chem. 2017, XX, 1—7

Catalyst for Synthesis of 1,2,3-Triazoles in Water
Table 3 One-pot synthesis of triazoles from alkyl halides, NaN3 and alkynesa
N
R1
N
copper(II) acetylacetonate (2 mol%)
H2O, 100 oC
N
R2
R1X
NaN3
+
+
R2
Entry
1
R1X
Product
Time/min
70
Yieldb/%
89
2
3
4
5
6
7
8
9
60
45
90
88
84
80
90
88
86
81
90
O
200
100
75
Cl
Cl
180
160
O
N
N
O
N
O
10
11
210
150
82
80
a Reaction conditions:. terminal alkyne (1.0 mmol), sodium azide (1.2 mmol), alkyl halide (1.0 mmol), Cu(acac)2 (2 mol%), H2O (2.0 mL)
and 100 ℃. b Isolated yields.
(Nos. 152102210285 and 152102310312), the Innova-
tive Talents Program of Henan Province (Nos.
164100510015 and 174100510025), the Produc-
tion-Learning-Research Cooperation Project of Henan
Province (Nos. 122107000014, 142107000081 and
122107000014), the Foundation of Henan Educational
Committee (Nos. 14A350005 and 16A350015), the
suitable for one-pot three-component reactions among
alkyl halides, NaN3 and alkynes.
Acknowledgement
This work was financially supported by the Key
Scientific and Technological Project of Henan Province
Chin. J. Chem. 2017, XX, 1—7
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Jiang et al.
COMMUNICATION
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