Cu(II)-CMC: A mild, efficient and recyclable catalyst for the oxidative alkyne homocoupling reaction

Article abstract of DOI:10.1515/znb-2017-0009

Cu(II) heterogenized on sodium carboxymethyl cellulose (Na-CMC) has been thoroughly characterized by different techniques. Cu(II)-CMC has been applied for the first time in the homocoupling reaction of a variety of terminal alkynes. The catalyst furnished

Full text of DOI:10.1515/znb-2017-0009

Z. Naturforsch. 2017; 72(8)b: 549–554
YCuuqin(IJiIa)n-g*C, NMiu CGu:o,aXiymongilLid, Y,ameinffSiucn iaendnWteiaweni Zdhanrge*cyclable
catalyst for the oxidative alkyne homocoupling
reaction
DOI 10.1515/znb-2017-0009
numerous other fields, such as supramolecular switches
[14], carbon-rich materials [15], organic conductors [16],
and so on.
Received January 13, 2017; accepted June 2, 2017
Abstract: Cu(II) heterogenized on sodium carboxymethyl
cellulose (Na-CMC) has been thoroughly characterized
by different techniques. Cu(II)-CMC has been applied for
the first time in the homocoupling reaction of a variety of
terminal alkynes. The catalyst furnished good to excel-
lent yields of the desired products and could be reused
six times without loss of catalytic activity. The Cu(II)-CMC
catalysis protocol is a new efficient route to synthesize
1,3-diynes under mild conditions.
The homocoupling reaction of terminal alkynes can
be performed efficiently through catalysis by a combi-
nation of palladium and copper salts [17–19]. However,
palladium reagents are very expensive, sensitive to air
and require additional ligands in the reaction. In recent
years, great efforts have been devoted to the development
of copper-mediated homocoupling reactions of terminal
alkynes under palladium-free conditions due to their eco-
nomic advantages and environmental friendliness. The
Keywords: Cu(II)-CMC; 1,3-diyne; heterogeneous cataly- copper-catalytic systems include Cu(I) complexes [20–
sis; homocoupling reaction; reusable.
27], Cu(II) complexes [28–35] and metallic copper [36].
Cu(II) complexes are preferably used as catalytic systems
due to the susceptibility of Cu(I) salts to redox processes.
They require, however, the utilization of (often foul smell-
ing) nitrogen bases, ligands and/or other additives to
protect and stabilize the active Cu(I) catalysts. Most of
the reported Cu(II) catalytic systems are homogeneous
and have shortcomings in that the separation of cata-
lysts and products and the recycling of the catalysts are
difficult. A few Cu(II) complexes heterogenized on inor-
ganic supports have been reported as catalytic systems
for the oxidative homocoupling of terminal alkynes, such
as CuAl-LDH [33], Cu(OH)x/TiO2 [37], Cu(OH)x/OMS-2 [38],
Cu(II)-clay [39] and Cu(II)-SBA-15 [40]. However, there are
certain drawbacks to these Cu(II)-based heterogeneous
catalysts, such as the requirement of bases, pure oxygen
(1 atm) or long preparation time. Therefore, simpler yet
effective and environmentally benign Cu(II)-based het-
erogeneous catalysts for homocoupling reactions are still
desirable.
Sodium carboxymethyl cellulose (Na-CMC) is an
important and very useful carboxylate-modified ether
derivative from CMC. Its water solubility, non-toxicity,
good availability and biodegradation combined with low
cost favor its use in diverse applications [41–44], such
as drug delivery [45], antibacterial materials [46] and
sequestering agents for the removal of heavy metals [47].
Another interesting application is to explore the possibil-
ity of using CMC-containing metal complexes directly for
organic reactions. As far as we know, there is no report
1 Introduction
The copper-mediated Glaser-type homocoupling reaction
of terminal alkynes is the most promising method for the
synthesis of 1,3-diynes. It was first reported by Glaser in
1869 [1]. The 1,3-diynes synthesized by Glaser-type cou-
pling reactions are an important class of building blocks
in numerous natural products [2–7], pharmaceutical inter-
mediates and bioactive compounds [2, 8–13] with anti-
HIV, antifungal, anticancer activities, etc. Moreover, the
application of 1,3-diynes chemistry has been extended to
*Corresponding authors: Yuqin Jiang and Weiwei Zhang, Henan
Engineering Laboratory of Chemical Pharmaceuticals and 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, P.R. China, e-mail: jiangyuqin@htu.cn (Y. Jiang);
2016022@htu.edu.cn (W. Zhang)
Niu Guo: Henan Engineering Laboratory of Chemical
Pharmaceuticals and 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, P.R. China
Xiyong Li and Yamin Sun: Weihai Ocean Vocational College, Weihai,
P.R. China
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ꢀY. Jiang et al.: Cu(II)-CMC catalysis protocol
10
20
30
40
50
60
70
80 10
20
30
40
50
60
70
80
2-θ
2-θ
Fig. 1:ꢀX-ray diffraction spectra of CMC (left) and Cu(II)-CMC (right).
Fig. 2:ꢀThe representative SEM images for CMC (left) and Cu(II)-CMC (right).
Cu(II)-CMC
on using copper-containing CMC in the oxidative alkyne
homocoupling reaction. Herein, we report an environ-
mentally friendly and highly efficient method for the oxi-
dative alkyne homocoupling under mild conditions with
Cu(II)-CMC as a catalyst.
2
Solvent, air, ∆
Scheme 1:ꢀThe model reaction for optimizing reaction conditions.
phenylacetylene (1.0 mmol), catalyst (10 mol%), solvent
(2.0 mL), reaction temperature (90°C), reaction time (2 h)
and the presence of atmospheric oxygen. The reaction
was carried out in DMSO, DMF, toluene, H2O, 1,4-dioxane
and CH3CN. As is shown in Table 1 (entries 1–6), for the
catalysis with Cu(II)-CMC high-polarity solvents exhibited
2 Results and discussion
The Cu(II)-CMC was prepared according to a previously
reported procedure [48] and characterized by X-ray dif-
fraction (XRD) (Fig. 1), scanning electron microscopy
(SEM) (Fig. 2) and inductively coupled plasma mass
spectrometry (ICP-MS). The XRD patterns of CMC and the
Cu(II)-CMC catalyst are shown in Fig. 1. They show largely
crystalline Na-CMC but amorphous Cu(II)-CMC, which is
consistent with the SEM images in Fig. 2. The percentage
of copper in Cu(II)-CMC was found to be 11.6% as deter-
mined by ICP-MS.
Table 1:ꢀScreening solvent for the homocoupling reaction of
phenylacetylene.
Entry
Catalyst
Solvent
Time (h)
Yield (%)a
1
2
3
4
5
6
Cu(II)-CMC
Cu(II)-CMC
Cu(II)-CMC
Cu(II)-CMC
Cu(II)-CMC
Cu(II)-CMC
DMSO
DMF
2
2
2
2
2
2
91
60
Toluene
1,4-Dioxane
H2O
15
10
Trace
Trace
First, the reaction conditions of the homocoupling
of phenylacetylene were optimized, which was taken as
the model reaction (Scheme 1). For the screening of suit-
CH3CN
able solvents, the reaction conditions were set as follows: aIsolated yields.
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Y. Jiang et al.: Cu(II)-CMC catalysis protocolꢂ
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significant advantages over low-polarity solvents, which with Cu(OAc)2ꢀ·ꢀH2O (10 mol%) as a catalyst is 96%, much
is consistent with previous reports [30, 35, 40]. Among the higher than with CuSO4ꢀ·ꢀ5H2O (10 mol%; see above). The
−
tested solvents, the highest yield was obtained in DMSO AcO in Cu(OAc)2ꢀ·ꢀH2O acts as the base in the alkyne homo-
(91%, Table 1, entry 1). The yield obtained in DMF was coupling reaction [49]. As there are many carboxylate rests
moderate 60% (Table 1, entry 2). The yields obtained in in CMC, in Cu(II)-CMC likewise, they are supposed to act
toluene and 1,4-dioxane were 15% (Table 1, entry 3) and as the base in the alkyne homocoupling reaction.
10% (Table 1, entry 4), respectively. The lowest yields
On the basis of the present results and the literature
(Table 1, entries 5 and 6) among the tested solvents were reports [40], a reaction mechanism is proposed for the
obtained in H2O and CH3CN. Therefore, DMSO was selected oxidative homocoupling of terminal alkynes to 1,3-diyne
as the optimum reaction solvent.
derivatives with Cu(II)-CMC as a catalyst, which is shown
Secondly, the reaction temperature was optimized for in Scheme 2.
the model reaction in DMSO. When the reaction tempera-
Having the optimized reaction conditions in hand,
ture was elevated from 90°C to 100°C or 110°C, the yields a variety of terminal alkynes with different functional
were almost identical (reaction time 2 h). When decreas- groups were tested as reagents in order to evaluate the
ing the temperature to 80°C, the yield was reduced to scope of the protocol. As shown in Table 2, the oxidative
60% in 7 h. Upon further reducing the reaction tempera- homocoupling of phenyl acetylenes containing electron-
ture, only 27% yield was obtained at 70°C and traces were donating (methyl, amino, ethyl, n-propyl, n-pentyl, -oxym-
obtained at 60°C–70°C in 7 h. Hence, 90°C was selected ethyl) as well as electron-withdrawing substituents (-F, -Cl)
as the optimum reaction temperature. Furthermore, the proceeded smoothly to afford the corresponding 1,3-diyne
catalyst loading was also investigated. When the cata- derivatives in 79–95% yield (Table 2, entries 1–8). For ali-
lyst loading was reduced to 5 mol%, the obtained yield in phatic terminal alkynes the yields of the corresponding
4 h was 53%. When the catalyst loading was changed to 1,3-diynes are slightly lower (Table 2, entries 9–11).
15 mol%, the product yield was 91% (2 h) which was the
same as that obtained with catalysis by 10 mol% Cu(II)-
CMC. Finally, according to the results mentioned above,
the optimized reaction conditions for the model reaction
3 Conclusions
were phenylacetylene (1.0 mmol), Cu(II)-CMC (10 mol%)
In summary, we have developed an efficient heterogene-
and DMSO (2.0 mL) at 90°C in the presence of air.
ous copper(II)-catalyzed protocol for the homocoupling
The lifetime and reusability of a heterogeneous cata-
reaction of terminal alkynes in DMSO using Cu(II)-CMC as
lytic system are particularly crucial factors. The recycla-
a reusable catalyst. The protocol is not only suitable for
bility of Cu(II)-CMC was investigated by the following
phenyl acetylenes derivatives, but also for aliphatic termi-
procedures. After the completion of the reaction, Cu(II)-
nal alkynes.
CMC was filtrated and washed with little DMSO. The so
obtained Cu(II)-CMC was directly used for the next cycle.
The activity of Cu(II)-CMC was constant even after six
2R
cycles.
Cu2+CMC
In order to investigate the role of CMC in the oxidative
alkyne homocoupling reaction, further experiments were
Step I
R
R
carried out. Reactions were performed using CuSO4ꢀ·ꢀ5H2O,
Na-CMC and CuSO4ꢀ·ꢀ5H2O/Na-CMC as catalysts, respec-
tively, instead of Cu(II)-CMC. It was found that when
catalyzed by 10 mol% CuSO4ꢀ·ꢀ5H2O, only 50% yield was
obtained, much less than with Cu(II)-CMC (91%). In this
case the final reaction mixture became homogeneous. The
reaction with Na-CMC alone gave no product. Catalysis by
CuSO4ꢀ·ꢀ5H2O (10 mol%) in the presence of Na-CMC gave
the same yield as with Cu(II)-CMC in 2 h. It is obvious that
Na-CMC greatly improves the catalytic efficiency of Cu(II)
salts in the alkyne homocoupling reaction.
R
Step III
CMCCu2+
R
Cu2+CMC
R
R
Step II
CMCCu+
Cu+CMC
AsisreportedbyJiaandco-workers[35], theyieldofthe
homocoupling reaction of 1-(n-propyl)-4-ethynylbenzene Scheme 2:ꢀProposed reaction mechanism for the Cu(II)-CMC catalyst.
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552ꢀ ꢀY. Jiang et al.: Cu(II)-CMC catalysis protocol
Table 2:ꢀOxidative homocoupling activity of Cu(II)-CMC on different terminal alkynes.a
Cu(II)-CMC
2 R
R
R
DMSO,90°C
Entry
Alkyne
Product
Time (h)
Yield (%)b
1
2
91
2
3
2.5
90
93
2
n-C3H7
n-C3H7
n-C3H7
4
5
6
1.5
3
95
83
89
n-C5H11
n-C5H11
n-C5H11
F
F
F
6
7
3
5
79
91
MeO
MeO
OMe
8
Cl
Cl
Cl
O
O
O
9
2.5
81
78
O
O
O
10
4
Meo
MeO
OMe
O
O
O
11
6
57
CF3
CF3
CF3
aReaction conditions: terminal alkynes (1.0 mmol), Cu(II)-CMC (10 mol%), DMSO (2.0 mL) and at 90°C in air; bisolated yields.
solution. The mixture was constantly stirred during the
copper sulfate addition. After completion of the addi-
tion, the stirring was continued for 5 h at room tempera-
ture. The obtained slurry was centrifugated and washed
several times with distilled water in order to remove
residual Cu(II) ions. Cu(II)-CMC was finally obtained by
freeze-drying.
4 Experimental section
4.1 General
All reagents were purchased from commercial sources
and used without further treatment, unless otherwise
1
indicated. The products were characterized by H NMR
and 13C NMR (Bruker Avance/400) with CDCl3 as a solvent
and tetramethylsilane as an internal standard. Data are
represented as follows: chemical shift, integration, mul- 4.3 General procedure for the synthesis
tiplicity (sꢀ=ꢀsinglet, dꢀ=ꢀdoublet, ddꢀ=ꢀdouble of doublets,
of 1,3-diynes
tꢀ=ꢀtriplet, qꢀ=ꢀquartet, mꢀ=ꢀmultiplet, brꢀ=ꢀbroad) and cou-
pling constants (J) in hertz (Hz).
To a stirred solution of the terminal alkynes (1.0 mmol)
in DMSO (2.0 mL), Cu(II)-CMC (10 mol%) was added in
the open air. The resulting mixture was then warmed to
90°C in air. The process of the reaction was monitored by
thin-layer chromatography. After completion, the reaction
4.2 Catalyst preparation
A copper sulfate solution (10% CuSO4ꢀ·ꢀ5H2O 150 mL) mixture was cooled to room temperature and diluted with
was added dropwise to 300 mL of a 1% Na-CMC ethyl acetate followed by the separation of the catalyst
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from the reaction mixture by filtration under reduced 4.3.6 1,4-Bis(4-fluorophenyl)buta-1,3-diyne (6) [39]
pressure. The filtrate was washed with brine solution,
dried over anhydrous Na2SO4 and the ethyl acetate was 1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.53–7.50 (m, 4H, Ar-H),
13
removed under reduced pressure. The residue was then 7.04 (t, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H). – C NMR (100 MHz, CDCl3):
purified by column chromatography on silica gel using δꢀ=ꢀ164.3–161.8 (d, Jꢀ=ꢀ250.0 Hz) 134.6–134.5 (d, Jꢀ=ꢀ10.0 Hz),
petroleum ether as eluent to afford the corresponding 1,3- 117.8, 116.0–115.8 (d, Jꢀ=ꢀ20.0 Hz), 80.4, 73.5.
diynes. All of the products are known and were charac-
terized by comparison of their spectral data with those of
authentic samples.
4.3.7 1,4-Bis(p-methoxyphenyl)buta-1,3-diyne (7) [39]
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.46 (d, Jꢀ=ꢀ12.0 Hz, 4H,
4.3.1 1,4-Diphenylbuta-1,3-diyne (1) [40]
Ar-H), 6.85 (d, Jꢀ=ꢀ12.0 Hz, 4H, Ar-H), 3.82 (s, 6H, CH3-H).
13
– C NMR (100 MHz, CDCl3): δꢀ=ꢀ160.2, 134.1, 114.1, 113.9,
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.56 (dd, Jꢀ=ꢀ1.2 Hz, Jꢀ=ꢀ1.6 Hz,
81.26, 73.0, 55.4.
13
4H, Ar-H), 7.40–7.33 (m, 6H, Ar-H). – C NMR (100 MHz,
CDCl3): δꢀ=ꢀ132.5, 129.3, 128.5, 121.8, 81.6, 73.9.
4.3.8 1,4-Bis(3-chlorophenyl)buta-1,3-diyne (8) [40]
4.3.2 1,4-Ditolylbuta-1,3-diyne (2) [40]
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.52 (s, 2H, Ar-H), 7.43 (d,
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.43 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H), Jꢀ=ꢀ8.0 Hz, 2H, Ar-H), 7.38 (d, Jꢀ=ꢀ8.0 Hz, 2H, Ar-H), 7.30 (t,
7.15 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H), 2.37 (s, 6H, CH3-H). – 13C NMR Jꢀ=ꢀ6.0 Hz, 2H, Ar-H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ134.4,
(100 MHz, CDCl3): δꢀ=ꢀ139.5, 132.4, 129.3, 118.8, 81.6, 73.5, 21.7. 132.3, 131.1, 130.7, 129.8, 123.3, 80.6, 74.7.
4.3.3 1,4-Bis(4-ethylphenyl)buta-1,3-diyne (3) [40]
4.3.9 1,6-Diphenoxyhexa-2,4-diyne (9) [50]
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.45 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H),
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.32 (t, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H),
7.17 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H), 2.67 (q, Jꢀ=ꢀ8.0 Hz, 4H, CH2-H),
7.01 (t, Jꢀ=ꢀ8.0 Hz, 2H, Ar-H), 6.96 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H),
1.24 (t, Jꢀ=ꢀ8.0 Hz, 6H, CH3-H). – 13C NMR (100 MHz, CDCl3):
δꢀ=ꢀ145.8, 132.5, 128.1, 119.0, 81.6, 73.5, 29.0, 15.3.
13
4.76 (s, 4H, CH2-H). – C NMR (100 MHz, CDCl3): δꢀ=ꢀ157.4,
129.6, 121.8, 114.9, 74.7, 71.0, 56.2.
4.3.4 1,4-Bis(4-n-propylphenyl)buta-1,3-diyne (4) [35]
4.3.10 1,6-Bis(4-methoxyphenoxy)hexa-2,4-diyne
(10) [51]
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.44 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H),
7.15 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H), 2.60 (t, Jꢀ=ꢀ8.0 Hz, 4H, CH2-H), 1H NMR (400 MHz, CDCl3): δꢀ=ꢀ6.90 (d, Jꢀ=ꢀ12.0 Hz, 4H,
1.69–1.60 (m, 4H, CH2-H), 0.94 (t, Jꢀ=ꢀ8.0 Hz, 6H, CH3-H). Ar-H), 6.84 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H), 4.70 (s, 4H, CH2-H),
13
– C NMR (100 MHz, CDCl3): δꢀ=ꢀ144.3, 132.4, 128.6, 119.0, 3.77 (s, 6H, CH3-H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ154.6,
81.6, 73.5, 38.1, 24.3, 13.8.
151.5, 116.2, 114.7, 74.9, 70.9, 57.1, 55.7.
4.3.5 1,4-Bis(4-n-pentylphenyl)buta-1,3-diyne (5) [39]
4.3.11 1,6-Bis(3-(trifluoromethyl)phenoxy)hexa-2,4-
diyne (11) [52]
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.44 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H),
7.15 (d, Jꢀ=ꢀ8.0 Hz, 4H, Ar-H), 2.61 (t, Jꢀ=ꢀ8.0 Hz, 4H, CH2-H), 1H NMR (400 MHz, CDCl3): δꢀ=ꢀ7.44 (t, Jꢀ=ꢀ8.0 Hz, 2H,
1.63–1.59 (m, 4H, CH2-H), 1.33–1.31 (m, 8H, CH2-H), 0.90 Ar-H), 7.29 (d, Jꢀ=ꢀ8.0 Hz, 2H, Ar-H), 7.19 (s, 2H, Ar-H), 7.14
(t, Jꢀ=ꢀ6.0 Hz, 6H, CH3-H). – 13C NMR (100 MHz, CDCl3): (d, Jꢀ=ꢀ4.0 Hz, 2H, CH2-H). – 13C NMR (100 MHz, CDCl3):
δꢀ=ꢀ144.5, 132.4, 128.6, 119.0, 81.6, 73.5, 36.0, 31.5, 30.9, 22.5, δꢀ=ꢀ157.4, 132.2, 131.8, 130.1, 125.1, 122.4, 118.6, 118.6, 118.5,
14.0.
118.1, 112.1, 112.0, 74.1, 71.4, 56.4.
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5 Supporting Information
1
13
The H and C NMR spectra of the products and enlarged
X-ray diffraction spectra and SEM images of CMC and
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