pubs.acs.org/joc
materials,3 and molecular recognition systems.4 They are
Transition-Metal-Free Homocoupling
of 1-Haloalkynes: A Facile Synthesis of Symmetrical
1,3-Diynes
obtained either by Cu-mediated homocoupling reactions in-
cluding Glaser coupling,5 Eglinton coupling,6 Hay coupling,7
and related modified methods,8,9 or by Pd-catalyzed homo-
coupling reactions.10,11 Compared to the copper and palla-
dium catalysis other transition-metal mediated homocoupling
reactions for the synthesis of 1,3-diynes are still limited.12
However, transition-metal reagents are often expensive and
poisonous, and they often required air-sensitive and expensive
phosphine ligand and amine reagent. Few studies are focused
on the formation of 1,3-diynes without transition metal.13 One
example is the transition-metal-free oxidative homocoupling
reaction of alkynylmagnesium compounds reported by
Knochel.13a For the environmental and economical consid-
eration, development of a transition-metal-free system for
the synthesis of 1,3-diynes is an attractive route.
Zhengwang Chen, Huanfeng Jiang,* Azhong Wang, and
Shaorong Yang
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510640,
People’s Republic of China
Received June 22, 2010
Haloalkynes are high-value synthons widely used in synthetic
organic chemistry.14,15 On the basis of these promising potenti-
alities of 1-haloalkynes, herein we present a highly efficient
protocol for the synthesis of symmetrical 1,3-diynes from
1-haloalkynes without any transition-metal, base, and oxidant.
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K.; Ando, J.; Atsunori Mori, A.; Hiyama, Y. J. Org. Chem. 2000, 65, 1780–
Symmetrical 1,3-diyne compounds can be easily synthe-
sized via a transition-metal-free homocoupling reaction
of 1-haloalkynes without base and oxidant. The method
shows excellent functional group compatibility and high
yields.
~
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1,3-Diyne compounds are versatile building blocks in the
construction of linearly π-conjugated acetylenic oligomers
and polymers,1 natural products,2 electronic and optical
€
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Published on Web 08/31/2010
DOI: 10.1021/jo101216m
r
2010 American Chemical Society