Categories: C-C Bond Formation > Chains > Alkynes >
Synthesis of substituted 1,3-diynes
Name Reactions
Recent Literature
Air Tolerant Cadiot-Chodkiewicz and Sonogashira Cross-Couplings
A. K. K. Fung, M. J. Sowden, M. L. Coote, M. S. Sherburn, Org. Lett., 2023, 25,
8145-8149.
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.
Iron catalyzes a cross-coupling of 1-bromoalkynes with terminal alkynes to
generate unsymmetrical 1,3-butadiynes in water under air. Reactions of
1-bromoalkynes derived from less acidic terminal alkynes with more acidic
counterparts offer greatly enhanced yields and selectivity. A coupling of
1-bromoalkynes and trimethylsilyl-protected 1,3-butadiynes provides
1,3,5-hexatriynes.
Y.-A. Liao, W.-S. Peng, L.-J. Liu, T.-Y. Ye, J.-H. Fu, Y.-T. Chan, F.-Y. Tsai, J. Org. Chem., 2022, 87,
13698-13707.
Recyclable Polystyrene-Supported Copper Catalysts for the Aerobic Oxidative
Homocoupling of Terminal Alkynes
S. Yan, S. Pan, T. Osako, Y. Uozumi,
Synlett, 2016, 27, 1232-1236.
Gold-catalyzed oxidative cross-coupling of alkynes to unsymmetrical diynes has
been achieved in the presence of 1,10-Phen as ligand and PhI(OAc)2 as
oxidant giving the desired cross-coupled conjugated diynes in excellent
heteroselectivity (>10:1), in good to excellent yields, and with large substrate
tolerability.
H. Peng, Y. Xi, N. Ronaghi, B. Dong, N. G. Akhmedov, X. Shi, J. Am. Chem. Soc., 2014,
136, 13174-13177.
Low loadings of imidazol(in)ium aurates catalyze a simple and efficient oxidative coupling of terminal alkynes. This approach displays high functional group tolerance and leads
to a broad range of 1,3-diyne compounds in good yields in air under mild and sustainable
conditions.
X. Ma, N. V. Tzouras, M. Peng, K. Van Hecke, S. P. Nolan, J. Org. Chem., 2022, 87,
4883-4893.
An efficient cross-coupling of alkynyl bromides and boronates to produce
unsymmetric 1,3-diynes is catalyzed by CuFe2O4
nanoparticles in dimethyl carbonate. The protocol also enables a coupling of
alkynyl bromides and alkenyl boronic acids to provide conjugated 1,3-enynes. The
catalyst was easily separated by an external magnet and recycled 10 times.
S. Ahammed, D. Kundu, B. C. Ranu, J. Org. Chem., 2014,
79, 7391-7398.
An efficient Sonogashira coupling of terminal alkynes and styrenyl bromides is
catalyzed by hydroxyapatite-supported copper(I). Trans-styrenyl bromides
produce trans-enyne products, whereas cis-styrenyl bromides lead
to unsymmetric 1,3-diynes by the cross coupling of terminal alkyne and the
alkyne generated from the cis-styrenyl bromide.
D. Saha, T. Chatterjee, M. Mukherjee, B. C. Ranu, J. Org. Chem., 2012,
77, 9379-9383.
In a copper-catalyzed decarboxylative coupling reaction, a broad range of aryl,
alkenyl, alkynyl, and alkyl substituted 1,1-dibromo-1-alkenes react smoothly
with aryl and alkyl substituted potassium propiolates to produce unsymmetrical
1,3-diynes and 1,3,5-triynes with high selectivity and good functional group
compatibility.
Z. Huang, R. Shang, Z.-R. Zhang, X.-D. Tan, X. Xiao, Y. Fu, J. Org. Chem., 2013,
78, 4551-4557.
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 Rh(I)-catalyzed C-C activation of diynones enables the synthesis of
symmetrical and unsymmetrical conjugated diynes through decarbonylation. This
C-C cleavage strategy takes advantage of the innate reactivity of conjugated
ynones without relying on any ring strain or auxiliary directing group.
A. Dermenci, R. E. Whittaker, G. Dong, Org. Lett., 2013,
15, 2242-2245.
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.
Nonafluorobutanesulfonyl azide is a highly efficient reagent for an extremely
fast copper-catalyzed coupling of terminal alkynes to give symmetrical and
unsymmetrical 1,3-diynes in good to excellent yields and with good functional
group compatibility. In addition, nonafluorobutanesulfonyl azide is a superior
and safe alternative to other electrophilic azide reagents in use today.
J. R. Suárez, D. Collado-Sanz, D. J. Cárdenas, J. L. Chiara, J. Org. Chem.,
2015,
80, 1098-1106.
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.
Related
A Strictly "Pair"-Selective Synthesis of Conjugated Diynes via Pd-Catalyzed
Cross Coupling of 1,3-Diynylzincs: A Superior Alternative to the
Cadiot-Chodkiewicz Reaction
E.-i. Negishi, M. Hata, C. Xu,
Org. Lett., 2000, 2, 3687-3689.