N-Heterocyclic Carbene/Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions in Aqueous Medium

Year 2019, , 13 - 20, 01.03.2019

Murat Kaloğlu

https://doi.org/10.19113/sdufenbed.440237

Abstract

In this study, a series of ether-functionalized benzimidazolium
salts as N-heterocyclic carbene (NHC)
ligands were synthesized and their structures characterized by ¹H
NMR, ¹³C NMR, FT-IR, and elemental analysis techniques. The in situ formed [PdX₂(NHC)₂] complexes from the interaction
of Pd(OAc)₂ with NHC ligands were used as catalyst in the
Suzuki-Miyaura cross-coupling reactions between phenylboronic acid and aryl chlorides under mild reaction conditions in aqueous
media. In situ formed [PdX₂(NHC)₂] catalysts
showed high catalytic activity for electron-donating, electron-drawing or
sterically hindered aryl chlorides.

Keywords

N-Heterocyclic carbene, Palladium, Suzuki-Miyaura cross-coupling, in situ formed catalyst

Sulu Ortamda N-Heterosiklik Karben/Palladyum Katalizli Suzuki-Miyaura Çapraz-Eşleşme Tepkimeleri

Abstract

Bu çalışmada, N-heterosiklik
karben (NHC) ligandı olarak bir seri eter-fonksiyonalize benzimidazolyum tuzu
sentezlendi ve yapıları ¹H NMR, ¹³C
NMR, FT-IR ve element analizi yöntemleri ile karakterize edildi. NHC ligandları
ile Pd(OAc)₂’ın etkileşiminden in
situ oluşturulan [PdX₂(NHC)₂]
kompleksleri, sulu ortamda ve ılımlı koşullar altında fenilboronik asit
ve aril klorürlerin Suzuki-Miyaura çapraz-eşleşme tepkimelerinde katalizör
olarak kullanıldı. In situ
oluşturulan [PdX₂(NHC)₂] katalizörleri, elektron verici,
elektron çekici veya sterik engelli aril klorürler için yüksek katalitik
aktivite gösterdi.

Keywords

N-Heterosiklik karben, Palladyum, Suzuki-Miyaura çapraz-eşleşmesi, in situ oluşturulmuş katalizör

References

• [1] Hassan, J., Sévignon, M., Gozzi, C., Schulz, E., Lemaire, M. 2002. Aryl-Aryl Bond Formation One Century After the Discovery of the Ullmann Reaction. Chemical Reviews, 102(2002), 1359-1470.
• [2] Eicher, T., Hauptmann, S., Speicher, A. 2012. The Chemistry of Heterocycles: Structures, Reactions, Synthesis, and Applications. 3nd, completely revised and enlarged edition. WILEY-VCH Verlag GmbH&Co. KGaA, Weinheim, 646s.
• [3] Li, J. J., Gribble, G. W. 2007. Palladium in Heterocyclic Chemistry-A guide to the Synthetic Chemist. 2nd edition. Elsevier Ltd., Oxford, 658s.
• [4] Beller, M., Bolm, C. 2004. Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals. 2nd revised and enlarged edition. WILEY-VCH Verlag GmbH&Co. KGaA, Weinheim, 1344s.
• [5] de Meijere, A., Diederich, F. 2014. Metal-Catalyzed Cross-Coupling Reactions. 2nd, completely revised and enlarged edition. WILEY-VCH Verlag GmbH&Co. KGaA, Weinheim, 938s.
• [6] Alberico, D., Scott, M. E., Lautens, M. 2007. Aryl-Aryl Bond Formation by Transition-Metal-Catalyzed Direct Arylation. Chemical Reviews, 107(2007), 174-238.
• [7] Nicolaou, K. C., Bulger, P. G., Sarlah, D. 2005. Palladium-Catalyzed Cross-Coupling Reactions in Total Synthesis. Angewandte Chemie International Edition, 44(2005), 4442-4489.
• [8] Heck, R. F., Negishi, E., Suzuki, A. 2010. The Nobel Prize in Chemistry 2010. https://www.nobelprize.org/nobel_prizes/chemistry/laureates/2010/ (Erişim Tarihi: 02.07.2018).
• [9] Miyaura, N., Yamada, K., Suzuki, A. 1979. A New Stereospecific Cross-Coupling by the Palladium-Catalyzed Reaction of 1-Alkenylboranes with 1-Alkenyl or 1-Alkynyl Halides. Tetrahedron Letters, 20(1979), 3437-3440.
• [10] Miyaura, N., Suzuki, A. 1995. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. Chemical Reviews, 95(1995), 2457-2483.
• [11] Suzuki, A. 1999. Recent Advances in the Cross-Coupling Reactions of Organoboron Derivatives with Organic Electrophiles. Journal of Organometallic Chemistry, 576(1999), 147-168.
• [12] Littke, A. F., Fu, G. C. 2002. Palladium‐Catalyzed Coupling Reactions of Aryl Chlorides. Angewandte Chemie International Edition, 41(2002), 4176-4211.
• [13] Suzuki, A. 2002. Cross-Coupling Reactions via Organoboranes. Journal of Organometallic Chemistry, 653(2002), 83-90.
• [14] Deng, Y., Gong, L., Mi, A., Liu, H., Jiang, Y. 2003. Suzuki Coupling Catalyzed by Ligand-Free Palladium(II) Species at Room Temperature and by Exposure to Air. Synthesis, 3(2003), 337-339.
• [15] Anastas, P., Eghbali, N. 2010. Green Chemistry: Principles and Practice. Chemical Society Reviews, 39(2010), 301-312.
• [16] Li, C. -J., Chan, T. -H. 2007. Comprehensive Organic Reactions in Aqueous Media. 2nd edition. John Wiley&Sons, Inc., New York, 440s.
• [17] Sakurai, H., Sukuda, T., Hirao, T. 2002. Pd/C as a Reusable Catalyst for the Coupling Reaction of Halophenols and Arylboronic Acids in Aqueous Media. Journal of Organic Chemistry, 67(2002), 2721-2722.
• [18] Genet, J. -P., Savignac, M. 1999. Recent Developments of Palladium(0) Catalyzed Reactions in Aqueous Medium. Journal of Organometallic Chemistry, 576(1999), 305-317.
• [19] Parisot, S., Kolodziuk, R., Henry, C. G., Iourtchenko, A., Sinou, D. 2002. Glucosamine-Based Phosphines. Efficient Ligands in the Suzuki Cross-Coupling Reaction in Water. Tetrahedron Letters, 43(2002), 7397-7400.
• [20] Gürbüz, N., Özdemir, İ., Demir, S., Çetinkaya, B. 2004. Improved Palladium-Catalyzed Coupling Reactions of Aryl Halides Using Saturated N-Heterocarbene Ligands. Journal of Molecular Catalysis A: Chemical, 209(2004), 23-28.
• [21] Kaloğlu, M., Sémeril, D., Brenner, E., Matt, D., Özdemir, İ., Toupet, L. 2016. The Influence of Imidazolylidene Ligands with Bulky Resorcinarenyl Substituents on Catalysts for Suzuki-Miyaura Coupling. European Journal of Inorganic Chemistry, 7(2016), 1115-1120.
• [22] Yin, J., Rainka, M. P., Zhang, X. X., Buchwald, S. L. 2002. A Highly Active Suzuki Catalyst for the Synthesis of Sterically Hindered Biaryls:  Novel Ligand Coordination. Journal of American Chemical Society, 124(2002), 1162-1163.
• [23] McGuinness, D. S., Cavell, K. J. 2000. Donor-Functionalized Heterocyclic Carbene Complexes of Palladium(II):  Efficient Catalysts for C-C Coupling Reactions. Organometallics, 19(2000), 741-748.
• [24] Herrmann, W. A. 2002. N‐Heterocyclic Carbenes: A New Concept in Organometallic Catalysis. Angewandte Chemie International Edition, 41(2002), 1290-1309.
• [25] Hopkinson, M. N., Richter, C., Schedler, M., Glorius, F. 2014. An Overview of N-Heterocyclic Carbenes. Nature, 510(2014), 485-496.