Aqueous-Phase, Palladium-Catalyzed Suzuki Reactions under Mild Conditions


Water-soluble ionic liquid-supported diols have been used as phosphine-free ligands in Suzuki couplings of aryl idides/bromides/chlorides under mild conditions in aqueous solvent. It was found that 2,2-bis((1-hexylimidazolium)-mehyl) propane-1,3-diol hexafluorophosphate (4) in combination with palladium (II) salts gave the most significant catalyst. Suzuki couplings of aryl iodides/bromides occurred efficiently at room temperature in water/acetonitrile. Notably, the reactions of hydrophilic aryl bromides gave high yields in neat water. The catalyst PdCl2-4 was recycled five times in Suzuki couplings in water before catalyst activity began to significantly drop. The average yield of five cycles was >95% per cycle.

Share and Cite:

Y. Cai, G. Song, Z. Wu and J. Zhang, "Aqueous-Phase, Palladium-Catalyzed Suzuki Reactions under Mild Conditions," Green and Sustainable Chemistry, Vol. 3 No. 4A, 2013, pp. 1-5. doi: 10.4236/gsc.2013.34A001.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] N. Miyaura and A. Suzuki, “Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds,” Che- mical Reviews, Vol. 95, No. 7, 1995, pp. 2457-2483.
[2] A. Suzuki, “Recent Advances in the Cross-Coupling Reactions of Organoboron Derivatives with Organic Electrophiles, 1995-1998,” Journal of Organometallic Chemistry, Vol. 576, No. 1-2, 1999, pp. 147-168.
[3] R. B. Bedford, C. S. J. Cazin and D. Holder, “The Development of Palladium Catalysts for C-C and C-Heteroatom Bond Forming Reactions of Aryl Chloride Substrates,” Coordination Chemistry Reviews, Vol. 248, No. 21-24, 2004, pp. 2283-2321.
[4] C. Amatore and A. Jutand, “Anionic Pd(0) and Pd(II) Intermediates in Palladium-Catalyzed Heck and Cross-Coupling Reactions,” Accounts of Chemical Research, Vol. 33, No. 5, 2000, pp. 314-321.
[5] V. Calo, A. Nacci, A. Monopoli, A. Fornaro, L. Sabbatini, N. Cioffi and N. Ditaranto, “Heck Reaction Catalyzed by Nanosized Palladium on Chitosan in Ionic Liquids,” Organometallics, Vol. 23, No. 22, 2004, pp. 5154-5158.
[6] V. Calo, A. Nacci, A. Monopoli, E. Ieva and N. Cioffi, “Copper Bronze Catalyzed Heck Reaction in Ionic Liquids,” Organic Letters, Vol. 7, No. 4, 2005, pp. 617-620.
[7] D. Zhao, Z. Fei, R. Scopelliti and P. J. Dyson, “Synthesis and Characterization of Ionic Liquids Incorporating the Nitrile Functionality,” Inorganic Chemistry, Vol. 43, No. 6, 2004, pp. 2197-2205.
[8] N. Audic, H. Clavéier, M. Mauduit and J.-C. Guillemin, “An Ionic Liquid-Supported Ruthenium Carbene Complex: A Robust and Recyclable Catalyst for Ring-Closing Olefin Metathesis in Ionic Liquids,” Journal of the American Chemical Society, Vol. 125, No. 31, 2003, pp. 9248-9249.
[9] J. C. Xiao, B. Twamley and J. M. Shreeve, “An Ionic Liquid-Coordinated Palladium Complex: A Highly Efficient and Recyclable Catalyst for the Heck Reaction,” Organic Letters, Vol. 6, No. 21, 2004, pp. 3845-3847.
[10] D. Zhao, Z. Fei, T. J. Geldbach, R. Scopelliti and P. J. Dyson, “Nitrile-Functionalized Pyridinium Ionic Liquids: Synthesis, Characterization, and Their Application in Carbon-Carbon Coupling Reactions,” Journal of the American Chemical Society, Vol. 126, No. 48, 2004, pp. 15876-15882.
[11] R. Wang, J.-C. Xiao, B. Twamley and J. N. M. Shreeve, “Efficient Heck Reactions Catalyzed by A Highly Recyclable Palladium(II) Complex of a Pyridyl-Functionalized Imidazolium-Based Ionic Liquid,” Organic & Biomolecular Chemistry, Vol. 5, No. 4, 2007, pp. 671-678.
[12] R. Wang, M. M. Piekarski and J. N. M. Shreeve, “Pyra- zolyl-Functionalized 2-Methylimidazolium-Based Ionic Liquids and Their Palladium(II) Complexes as Recyclable Catalysts,” Organic & Biomolecular Chemistry, Vol. 4, No. 10, 2006, pp. 1878-1886.
[13] S. Li, Y. J. Lin, H. B. Xie, S. B. Zhang and J. N. Xu, “Bronsted Guanidine Acid-Base Ionic Liquids: Novel Reaction Media for the Palladium-Catalyzed Heck Reaction,” Organic Letters, Vol. 8, No. 3, 2006, pp. 391-394.
[14] J. C. Xiao and J. M. Shreeve, “Synthesis of 2,2’-Biimidazolium-Based Ionic Liquids: Use as a New Reaction Medium and Ligand for Palladium-Catalyzed Suzuki Cross-Coupling Reactions,” The Journal of Organic Chemistry, Vol. 70, No. 8, 2005, pp. 3072-3078.
[15] Y.Q. Cai, Y. Lu, Y. Liu and G. H. Gao, “Imidazolium Ionic Liquid-Supported Diol: an Efficient and Recyclable Phosphine-free Ligand for Palladium Catalyzed Heck Reaction,” Catalysis Letters, Vol. 119, No. 1-2, 2007, pp. 154-158.
[16] Y. Q. Cai, Y. Lu, Y. Liu, M. Y. He and Q. X. Wan, “Efficient Heck Reactions Catalyzed by a Palladium/Diol-Imidazolium Salt in Aerial Atmosphere,” Catalysis Com- munications, Vol. 9, No. 6, 2008, pp. 1209-1213.
[17] Y. Q. Cai and Y. Lu, “Efficient Palladium-Catalyzed Heck Reactions Mediated by the Diol-Functionalized Imi- dazolium Ionic Liquids,” Catalysis Communications, Vol. 10, No. 10, 2009, pp. 1390-1393.
[18] Y. Q. Cai, G. H. Song and X. Y. Zhou, “Aqueous-Phase, Palladium-Catalyzed Heck Reaction: The Significant Role of CN-Containing Counter Anion,” Chinese Journal of Chemistry, Vol. 30, No. 12, 2012, pp. 2819-2822.
[19] R. B. DeVasher, L. R. Moore and K. H. Shaughnessy, “Aqueous-Phase, Palladium-Catalyzed Cross-Coupling of Aryl Bromides under Mild Conditions, Using Water-Soluble, Sterically Demanding Alkylphosphines,” The Journal of Organic Chemistry, Vol. 69, No. 23, 2004, pp. 7919-7927.

Copyright © 2022 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.