Y. Liu et al.
a
Table 3. Homo-coupling of terminal alkyne catalyzed by PdCl
2
/1
(nos. 21463021, 21463022) and the Shihezi University Training
Programme for Distinguished Youth Scholars (no. 2014ZRKXJQ05).
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Entry
R/3
Product
Yield (%)
1
2
3
4
5
6
7
8
9
3-FC
3-ClC
3-MeC
3-MeOC
3-NH
4-FC
4-ClC
4-MeC
4-MeOC
4-CH CNC
4-C
4-PhC
6
H
4
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4b
4c
4d
4e
4f
99
89
98
85
65
86
87
99
98
83
70
95
95
95
68
47
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H
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4h
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6 4
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6 4
H
[
6
H
4
4j
10
11
12
13
14
15
16
2
6
H
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4 k
4l
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H
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C H
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H /3m
4m
4n
4o
4p
4q
3-Thiophyl/3n
Cyclopropyl/3o
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2
2
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Reaction conditions: alkyne, 1.0 mmol; PdCl
2
, 0.1 mol%; ligand 1,
2
0
.2 mol%; CuI, 2 mol%; NEt 1 mmol; DMF, 1 ml; room
3
,
temperature; 24 h; oxygen balloon.
b
Isolated yield.
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6
of para-substituted terminal alkynes with electron-donating as well
as electron-withdrawing substituents results in efficient homo-
coupling reactions and the corresponding products 3g–3m are
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The heteroaromatic alkyne species 3n proves to be another
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[
to aliphatic terminal alkynes. Ethynylcyclopropane (3o) and
ethynylcyclohexane (3p) are converted into the corresponding
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be less reactive, most notably due to the weaker acidity of the
acetylenic proton. The corresponding product 4q is obtained in
47% yield (Table 3, entry 16).
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In summary, we have established a simple, yet efficient approach
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2
oxidative homo-coupling of terminal alkynes at room temperature
in the presence of oxygen. The transformation proves to be efficient
and widely applicable using a variety of aromatic, heteroaromatic
and aliphatic alkynes. The desired symmetric 1,3-diynes are
obtained in moderate to excellent yields.
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Acknowledgments
Supporting information
We gratefully acknowledge financial support of this work by the
National Basic Research Program of China (973 Program:
Additional supporting information may be found in the online ver-
2012CB722603), the National Natural Science Foundation of China
sion of this article at the publisher’s web-site.
wileyonlinelibrary.com/journal/aoc
Copyright © 2015 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2015, 29, 736–738