Homocoupling of Terminal Alkynes Catalyzed by Copper Complexes of 1,10-Phenanthroline under Base- and Solvent-free Condition

Poh Wai Wai Chia


The concept of green chemistry is fast gaining traction nowadays and in line with the United Nations Sustainable Development Goals. In this manuscript, a simple yet efficient procedure in the synthesis of symmetrical 1,3-diynes using various alkynes catalyzed by copper under base-free and solvent-less condition is presented. With the improved protocol, the formation of homocoupled 1,3-diynes from different alkynes were afforded in good yields. The improved synthetic protocol is in compliance with the principles of green chemistry, which include recyclable catalytic system, avoid the use of base and mild homocoupling reaction condition. The improved protocol can be applied for the synthesis of many desirable compounds that is of interest to the academia and industries.


Alkynes; 1,3-Diynes; Green chemistry; 1,10-Phenantroline; Recyclable catalytic system.

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Balaraman, K. & Kesavan, V. (2010) Efficient copper (II) acetate catalyzed homo-and

heterocoupling of terminal alkynes at ambient conditions. Synthesis, 2010(20): 3461-3466.

Barot, N., Patel, S.B. & Kaur, H. (2016) Nitro resin supported copper nanoparticles: an effective heterogeneous catalyst for CN cross coupling and oxidative CC homocoupling. Journal of Molecular Catalysis A: Chemical, 423(1): 77-84.

Eckstein, B.J., Melkonyan, F.S., Zhou, N., et al. (2017) Buta-1, 3-diyne-based π-conjugated polymers for organic transistors and solar cells. Macromolecules, 50(4): 1430-1441.

Hay, A.S. (1962) Oxidative coupling of acetylenes. II1. Journal of Organic Chemistry, 27(9):


Jeon, S.J., Li, H.M. & Walsh, P.J. (2005) A green chemistry approach to a more efficient

asymmetric catalyst: Solvent-free and highly concentrated alkyl additions to ketones. Journal of American Chemical Society, 127(47): 16416–16425.

Kuhn, P., Alix, A., Kumarraja, M., et al. (2009) Copper–zeolites as catalysts for the coupling of terminal alkynes: An efficient synthesis of diynes. European Journal of Organic Chemistry, 2009(3): 423-429.

Li, C.J. & Chen, L. (2006) Organic chemistry in water. Chemical Society Reviews: 2006(35),


Li, D., Yin, K., Li, J. & Jia, X. (2008) CuI/iodine-mediated homocoupling reaction of terminal

alkynes to 1, 3-diynes. Tetrahedron Letters, 49(41): 5918-5919.

Li, J. & Jiang, H. (1999) Glaser coupling reaction in supercritical carbon dioxide. Chemical

Communications, 7(23): 2369-2370.

Li, J.H., Liang, Y. & Xie, Y.X. (2005) Efficient palladium-catalyzed homocoupling reaction and Sonogashira cross-coupling reaction of terminal alkynes under aerobic conditions. Journal of Organic Chemistry, 70(11): 4393-4396.

Liao, Y., Wei, T., Yan, T. & Cai, M. (2017) Recyclable [Ru2Cl3(p-cymene)2][PF6]/Cu(OAc)2/PEG-400/H2O system for oxidative annulation of alkynes by aniline derivatives: Green synthesis of indoles. Tetrahedron, 73(9): 1238-1246.

Ma, K.Q., Miao, Y.H., Li, X., et al. (2017) Discovery of 1, 3-diyne compounds as novel and potent antidepressant agents: synthesis, cell-based assay and behavioral studies. RSC Advances, 7(26): 16005-16014.

Naidu, S. & Reddy, S.R. (2017) A Green and Recyclable Copper and Ionic Liquid Catalytic

System for the Construction of Poly‐heterocyclic Compounds via One‐pot Tandem Coupling Reaction. ChemistrySelect, 2(3): 1196-1201.

Peng, H., Xi, Y., Ronaghi, N., et al. (2014) Gold-catalyzed oxidative cross-coupling of terminal alkynes: selective synthesis of unsymmetrical 1, 3-Diynes. Journal of American Chemical Society, 136(38): 13174-13177.

Sharifi, A., Abaee, M.S., Mokhtare, Z. & Mirzaei, M. (2014) Room temperature synthesis of 2H-1, 4-benzoxazine derivatives using a recoverable ionic liquid medium. Environmental Chemistry letters, 12(2): 365-370.

Sheng, W.B., Chen, T.Q., Zhang, M.Z., et al. (2016) Copper porphyrin-catalyzed aerobic oxidative coupling of terminal alkynes with high TON. Tetrahedron Letters, 57(15): 1641-1643.

Shi, W. & Lei, A. (2014) 1, 3-Diyne chemistry: synthesis and derivations. Tetrahedron Letters,

(17): 2763-2772.

Shi, X.L., Hu, Q., Wang, F., Zhang, W. & Duan, P. (2016) Application of the polyacrylonitrile fiber as a novel support for polymer-supported copper catalysts in terminal alkyne homocoupling reactions. Journal of Catalysis, 337(1), 233-239.

Simon, M.O. & Li, C.J. (2012) Green chemistry oriented organic synthesis in water. Chemical

Society Reviews, 41(4): 1415-1427.

Xiao, R., Yao, R. & Cai, M. (2012) Practical oxidative homo‐and heterocoupling of terminal

alkynes catalyzed by immobilized copper in MCM‐41. European Journal of Organic Chemistry, 2012(22): 4178-4184.

Xu, H., Wu, K., Tian, J., Zhu, L. & Yao, X. (2018) Recyclable Cu/C3N4 composite catalysed

homo-and cross-coupling of terminal alkynes under mild conditions. Green Chemistry, 20(4): 793-797.

Urgoitia, G., SanMartin, R., Herrero, M.T. & Domínguez, E. (2017) Efficient copper-free

aerobic alkyne homocoupling in polyethylene glycol. Environmental Chemistry Letters, 15(1): 157-164.

Yamaguchi, K., Kamata, K., Yamaguchi, S., Kotani, M. & Mizuno, N. (2008) Synthesis and structural characterization of a monomeric di-copper-substituted silicotungstate [γ-H2SiW10O36Cu2(μ-1, 1-N3)2]4− and the catalysis of oxidative homocoupling of alkynes. Journal of Catalysis, 258(1): 121-130.

Yao, P. (2013) Gold-catalysed homocoupling of alkynes. Journal of Chemical Research,

(3): 174-176.

Yuan, Y., Xie, Y., Zeng, C., et al. (2017) A recyclable AgI/OAc−catalytic system for the efficient synthesis of α-alkylidene cyclic carbonates: carbon dioxide conversion at atmospheric pressure. Green Chemistry, 19(13): 2936-2940.


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