Share This Article:

Heck Reactions with Ultralow Concentration of Transition Metals under Microwave Irradiation

Full-Text HTML XML Download Download as PDF (Size:143KB) PP. 1-6
DOI: 10.4236/gsc.2014.41001    4,250 Downloads   6,321 Views   Citations


The Heck coupling reactions of aryl halides and olefins were performed under the microwave assistance. Interestingly, the ultralow concentration of transition metals (in ppb) coming from the reactants could catalyze the Heck coupling reactions under microwave irradiation, without addition of any catalysts, ligands and phase-transfer agents. The influences of bases, solvents and temperature were discussed, and the reaction rate was enhanced largely in the mixed solvents of NMP and water due to the solubility of base in water.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

H. Wang, H. Cheng and F. Zhao, "Heck Reactions with Ultralow Concentration of Transition Metals under Microwave Irradiation," Green and Sustainable Chemistry, Vol. 4 No. 1, 2014, pp. 1-6. doi: 10.4236/gsc.2014.41001.


[1] R. F. Heck, “Palladium-Catalyzed Vinylation of Organic Halides,” In: Organic Reactions, Vol. 27, Wiley, New York, 1982, pp. 345-390.
[2] F. Y. Zhao, M. Shirai and M. Arai, “Palladium-Catalyzed Homogeneous and Heterogeneous Heck Reactions in NMP and Water-Mixed Solvents Using Organic, Inorganic and Mixed Bases,” Journal of Molecular Catalysis A: Chemical, Vol. 154, No. 1-2, 2000, pp. 39-44.
[3] M. T. Reetz, E. Westermann, R. Lohmer and G. Lohmer, “A Highly Active Phosphine-Free Catalyst System for Heck Reactions of Aryl Bromides,” Tetrahedron Letters, Vol. 39, No. 46, 1998, pp. 8449-8452.
[4] A. H. M. de Vries, J. Mulders, J. H. M. Mommers, H. J. W. Henderickx and J. G. de Vries, “Homeopathic Ligand-Free Palladium as a Catalyst in the Heck Reaction. A Comparison with a Palladacycle,” Organic Letters, Vol. 5, No. 18, 2003, pp. 3285-3288.
[5] L. M. Tao, Q. G. Li, W. Q. Liu, Y. Zhou and J. F. Zhou, “Water-Promoted Palladium-Catalysed Heck Cross-Coupling Reactions of Aryl Halides with Alkenes in TBAB,” Journal of Chemical Research, Vol. 35, No. 3, 2011, pp. 154-156.
[6] F. Y. Zhao, B. M. Bhanage, M. Shirai and M. Arai, “Heck Reactions of Iodobenzene and Methyl Acrylate with Conventional Supported Palladium Catalysts in the Presence of Organic and/or Inorganic Bases without Ligands,” Chemistry A European Journal, Vol. 6, No. 5, 2000, pp. 843-848.<843::AID-CHEM843>3.0.CO;2-G
[7] F. Y. Zhao, M. Shirai, Y. Ikushima and M. Arai, “The Leaching and Re-Deposition of Metal Species from and onto Conventional Supported Palladium Catalysts in the Heck Reaction of Iodobenzene and Methyl Acrylate in N-Methylpyrrolidone,” Journal of Molecular Catalysis A: Chemical, Vol. 180, No. 1-2, 2002, pp. 211-219.
[8] F. Y. Zhao, K. Murakami, M. Shirai and M. Arai, “Recyclable Homogeneous/Heterogeneous Catalytic Systems for Heck Reaction through Reversible Transfer of Palladium Species between Solvent and Support,” Journal of Catalysis, Vol. 194, No. 2, 2000, pp. 479-483.
[9] D. Dallinger and C. O. Kappe, “Microwave-Assisted Synthesis in Water as Solvent,” Chemical Reviews, Vol. 107, No. 6, 2007, pp. 2563-2591.
[10] R. Zhang, O. Sato, F. Y. Zhao, M. Sato and Y. Ikushima, “Heck Coupling Reaction of Iodobenzene and Styrene Using Supercritical Water in the Absence of a Catalyst,” Chemistry: A European Journal, Vol. 10, No. 6, 2004, pp. 1501-1506.
[11] X. G. Xie, J. P. Lu, B. Chen, J. J. Han, X. G. She and X. F. Pan, “Pd/C-Catalyzed Heck Reaction in Ionic Liquid Accelerated by Microwave Heating,” Tetrahedron Letters, Vol. 45, No. 4, 2004, pp. 809-811.
[12] D. E. Bergbreiter and S. Furyk, “Microwave Promoted Heck Reactions Using an Oligo (Ethylene Glycol)-Bound SCS Palladacycle under Thermomorphic Conditions,” Green Chemistry, Vol. 6, No. 6, 2004, pp. 280-285.
[13] D. Villemin and F. Caillot, “Microwave Mediated Palladium-Catalysed Reactions on Potassium Fluoride/Alumina without Use of Solvent,” Tetrahedron Letters, Vol. 42, No. 4, 2001, pp. 639-642.
[14] N. E. Leadbeater and M. Marco, “Transition-Metal-Free Suzuki-Type Coupling Reactions,” Angewandte Chemie International Edition, Vol. 42, No. 12, 2003, pp. 1407-1409.
[15] N. E. Leadbeater and M. Marco, “Transition-Metal-Free Suzuki-Type Coupling Reactions: Scope and Limitations of the Methodology,” Journal of Organic Chemistry, Vol. 68, No. 14, 2003, pp. 5660-5667.
[16] R. K. Arvela, N. E. Leadbeater, M. S. Sangi, V. A. Williams, P. Granados and R. D. Singer, “A Reassessment of the Transition-Metal Free Suzuki-Type Coupling Methodology,” Journal of Organic Chemistry, Vol. 70, No. 1, 2005, pp. 161-168.
[17] R. K. Arvela and N. E. Leadbeater, “Microwave-Promoted Heck Coupling Using Ultralow Metal Catalyst Concentrations,” Journal of Organic Chemistry, Vol. 70, No. 5, 2005, pp. 1786-1790.
[18] N. E. Leadbeater, “Fast, Easy, Clean Chemistry by Using Water as a Solvent and Microwave Heating: The Suzuki Coupling as an Illustration,” Chemical Communications, No. 23, 2005, pp. 2881-2902.
[19] J. Yan, M. Zhu and Z. S. Zhou, “Rapid Microwave-Promoted Catalyst- and Base-Free Suzuki-Type Coupling Reaction in Water,” European Journal of Organic Chemistry, Vol. 2006, No. 9, 2006, pp. 2060-2062.
[20] S. S. Yi, D. H. Lee, E. Sin and Y. S. Lee, “Chitosan-Supported Palladium(0) Catalyst for Microwave-Prompted Suzuki Cross-Coupling Reaction in Water,” Tetrahedron Letters, Vol. 48, No. 38, 2007, pp. 6771-6775.
[21] C. Schmoeger, T. Szuppa, A. Tied, F. Schneider, A. Stolle and B. Ondruschka, “Pd on Porous Glass: A Versatile and Easily Recyclable Catalyst for Suzuki and Heck Reactions,” Chemsuschem, Vol. 1, No. 4, 2008, pp. 339-347.
[22] B. K. Singh, N. Kaval, S. Tomar, E. Van der Eycken and V. S. Parmar, “Transition Metal-Catalyzed Carbon-Carbon Bond Formation Suzuki, Heck, and Sonogashira Reactions Using Microwave and Microtechnology,” Organic Process Research & Development, Vol. 12, No. 3, 2008, pp. 468-474.
[23] K. M. Dawood and M. M. El-Deftar, “Microwave-Assisted C-C Cross-Coupling Reactions of Aryl and Heteroaryl Halides in Water,” Arkivoc, Vol. 2010, No. 9, 2010, pp. 319-330.
[24] B. K. Allam and K. N. Singh, “An Efficient Phosphine-Free Heck Reaction in Water Using Pd(L-Proline)(2) as the Catalyst Under Microwave Irradiation,” Synthesis, Vol. 2011, No. 7, 2011, pp. 1125-1131.
[25] D. de L. Martins, H. M. Alvarez, L. C. S. Aguiar and O. A. C. Antunes, “Heck Reactions Catalyzed by Pd(0)-PVP Nanoparticles under Conventional and Microwave Heating,” Applied Catalysis A: General, Vol. 408, No. 1-2, 2011, pp. 47-53.
[26] A. K. Gupta, N. Singh and K. N. Singh, “Microwave Assisted Organic Synthesis: Cross Coupling and Multicomponent Reactions,” Current Organic Chemistry, Vol. 17, No. 5, 2013, pp. 474-490.
[27] A. R. Hajipour and F. Rafiee, “Microwave-Assisted Suzuki Cross-Coupling Reactions Using Dimeric Ortho-Palladated Complex of Tribenzylamine,” Organic Preparations and Procedures International, Vol. 45, No. 6, 2013, pp. 465-472.
[28] K. Kranjc and M. Kocevar, “From Conventional Reaction Conditions to Microwave-Assisted Catalytic Transformations of Various Substrates. State of the Art in 2012 (Part B: Catalysis),” Current Organic Chemistry, Vol. 17, No. 5, 2013, pp. 457-473.
[29] Y. K. Zhang, Z. L. Lv, H. Y. Zhong, M. F. Zhang, T. Zhang, W. N. Zhang and K. Li, “Efficient Heck Cross-Coupling of 3-Iodo-Benzopyrones with Olefins under Microwave Irradiation without Phosphine,” Tetrahedron, Vol. 68, No. 47, 2012, pp. 9777-9787.
[30] B. M. Choudary, S. Madhi, N. S. Chowdari, M. L. Kantam and B. Sreedhar, “Layered Double Hydroxide Supported Nanopalladium Catalyst for Heck-, Suzuki-, Sonogashira-, and Stille-Type Coupling Reactions of Chloroarenes,” Journal of the American Chemical Society, Vol. 124, No. 47, 2002, pp. 14127-14136.
[31] S. H. 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.

comments powered by Disqus

Copyright © 2018 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.