Categories: C-C Bond Formation > Chains > Alkynes >
Synthesis of substituted 1,3-diynes
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Recent Literature
A cross-coupling of terminal alkynes with 1-bromoalkynes in the presence of
copper(I) iodide and tris(o-tolyl)phosphine enables the synthesis of
unsymmetrical buta-1,3-diynes in good yields under simple and mild reaction
conditions. The scope and limitations of the cross-coupling reaction were
investigated.
S. Wang, L. Yu, P. Li, L. Meng, L. Wang, Synthesis, 2011,
1541-1546.
A new Pd-catalyzed protocol
realized the cross-coupling of a broad scope of terminal alkynes and haloalkynes
in good to excellent yields with high selectivities and without homocoupling
using a phosphine-olefin ligand. Electron-rich alkynes,
which are normally difficult substrates in Glaser couplings, could be employed
as either nucleophiles or electrophiles.
W. Shi, Y. Luo, X. Luo, L. Chao, H. Zhang, J. Wang, A. Lei, J. Am. Chem. Soc., 2008,
130, 14713-14720.
In the presence of palladium(II) acetate and copper(I) iodide, unsymmetrical
buta-1,3-diynes were selectively obtained from the reaction of (E)-1,2-diiodoalkenes
with terminal alkynes in moderate to good yields at room temperature. Using the
same conditions, the coupling of 2-ethynylphenol with (E)-1,2-diiodoalkenes
followed by a cyclization at 100°C gives ethynylbenzofurans.
Y. Liang, L.-M. Tao, Y.-H. Zhang, J.-H. Li, Synthesis, 2008,
3988-3994.
A carbenoid Fritsch-Buttenberg-Wiechell (FBW) rearrangement of a substituted
dibromoolefinic precursor is used to generate a lithium acetylide, and
subsequent trapping with carbon-based electrophiles provides a wide range of di-
and triynes. The lithium acetylide formed from the FBW reaction can also undergo
transmetalation to provide zinc, copper, tin, or platinum acetylides.
T. Luu, Y. Morisaki, N. Cunningham, R. R. Tykwinski, J. Org. Chem., 2007,
72, 9622-9629.
Efficient Copper(II) Acetate Catalyzed Homo- and Heterocoupling of Terminal
Alkynes at Ambient Conditions
K. Balaraman, V. Kesavan, Synthesis, 2010, 3461-3466.
K. Balaraman, V. Kesavan, Synthesis, 2010, 3461-3466.
A facile and environmentally friendly synthetic method for a variety of
symmetrical 1,3-diyne derivatives is based on a Pd/C-CuI-catalyzed homocoupling
reaction of terminal alkynes. The reaction was efficiently catalyzed by an
extremely low loading of Pd/C and CuI in the presence of molecular oxygen as the
oxidant without any phosphine ligands and bases.
T. Kurita, M. Abe, T. Maegawa, Y. Monguchi, H. Sajiki, Synlett, 2007,
2521-2524.
A palladium-catalyzed dimerization of terminal acetylenes with iodosylbenzene as oxidant allowed the preparation of various diynes in good yields in a short period of time at room temperature.
J. Yan, F. Lin, Z. Yang, Synthesis, 2007, 1301-1303.
