Synthesis, Characterization and Microwave-Promoted Catalytic Activity of Novel N-phenylbenzimidazolium Salts in Heck-Mizoroki and Suzuki-Miyaura Cross-Coupling Reactions under Mild Conditions
A number of novel benzimidazolium salts having aryl substituents such as N-phenyl, 4-chlorophenyl and various alkyl substituents were synthesized. Their microwave-assisted catalytic activities were evaluated in Heck-Mizoroki and Suzuki-Miyaura cross-coupling reactions using a catalytic system consisting of Pd(OAc) 2/K 2CO 3 in DMF/H 2O under mild reaction conditions with consistent high yields, except those of 2-bromopyridine.
References
[1]
Firouzabadi, H.; Iranpoor, N.; Kaazemi, F. Carbon-carbon bond formation via homocoupling reaction of substrates with a broad diversity in water using Pd(OAc)2 and agarose hydrogel as a bioorganic ligand, support and reductant. J. Mol. Cat. A: Chem. 2011, 348, 94–99.
[2]
Miyaura, N.; Suzuki, A. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. Chem. Rev. 2009, 95, 2457–2483, doi:10.1021/cr00039a007.
[3]
Suzuki, A. Carbon-carbon bonding made easy. Chem. Commun. 2005, 4759–4763, doi:10.1039/b507375h.
[4]
Ananikov, V.P.; Beletskaya, I.P. Toward the ideal catalyst: From atomic centers to a “Cocktail” of catalysts. Organometallics 2012, 31, 1595–1604, doi:10.1021/om201120n.
[5]
Alonso, F.; Beletskaya, I.P.; Yus, M. Non-conventional methodologies for transition-metal catalysed carbon-carbon coupling: A critical overview. Part 2: The Suzuki reaction. Tetrahedron 2008, 64, 3047–3101.
[6]
Beletskaya, I.P.; Cheprakov, A.V. The Heck reaction as a sharpening stone of palladium catalysis. Chem. Rev. 2000, 100, 3009–3066, doi:10.1021/cr9903048.
[7]
Molnár, á. Efficient, selective, and recyclable palladium catalysts in carbon-carbon coupling reactions. Chem. Rev. 2011, 111, 2251–2320.
[8]
Dawood, K.M.; Fayed, M.S.; Elkhalea, M.M. Heck and Suzuki cross-couplings of aryl and heteroaryl bromides in water using a new palladium(II)-complex. ARKIVOC 2009, xiii, 324–341.
[9]
Alonso, D.A.; Najera, C. Oxime-derived palladacycles as source of palladium nanoparticles. Chem. Soc. Rev. 2010, 39, 2891–2902, doi:10.1039/b821314n.
[10]
Li, C.-J.; Chen, L. Organic chemistry in water. Chem. Rev. 2006, 35, 68–82.
[11]
Dallinger, D.; Kappe, C.O. Microwave-assisted synthesis in water as solvent. Chem. Rev. 2007, 107, 2563–2591, doi:10.1021/cr0509410.
Liu, L.-J.; Wang, F.; Shi, M. Elimination of an alkyl group from imidazolium salts: Imidazole-Coordinated dinuclear monodentate NHC-Palladium complexes driven by self-assembly and their application in the Heck reaction. Eur. J. Inorg. Chem. 2009, 2009, 1723–1728, doi:10.1002/ejic.200801207.
[14]
Kantchev, E.A.B.; O’Brien, C.J.; Organ, M.G. Palladium complexes of N-heterocyclic carbenes as catalysts for cross-coupling reactions—A synthetic chemist’s perspective. Angew. Chem. Int. Ed. 2007, 46, 2768–2813, doi:10.1002/anie.200601663.
[15]
Linninger, C.S.; Herdtweck, E.; Hoffmann, S.D.; Herrmann, W.A. A new palladium(II) complex of a functionalized N-heterocyclic carbene: Synthesis, characterization and application in Suzuki-miyaura cross-coupling reactions. J. Mol. Struct. 2008, 890, 192–197, doi:10.1016/j.molstruc.2008.05.037.
Mercan, D.; ？etinkaya, E.; ？etinkaya, B. Influence of CH3 substituents on tetrahydropyrimidin-2-ylidene: Sigma-donating properties and in situ catalytic activities of precursor salts/Pd(OAc)2 system for C–C coupling reactions. J. Organomet. Chem. 2011, 696, 1359–1366.
[18]
Korolev, D.N.; Bumagin, N.A. An improved protocol for ligandless Suzuki-Miyaura coupling in water. Tetrahedron Lett. 2006, 47, 4225–4229, doi:10.1016/j.tetlet.2006.04.039.
[19]
Tang, Y.-Q.; Chu, C.-Y.; Zhu, L.; Qian, B.; Shao, L.X. N-Heterocyclic carbene-Pd(II) complex derived from proline for the Mizoroki-Heck reaction in water. Tetrahedron 2011, 67, 9479–9483, doi:10.1016/j.tet.2011.10.033.
[20]
Liu, C.; Ni, Q.; Hu, P.; Qui, J. Oxygen-promoted PdCl2-catalyzed ligand-free Suzuki reaction in aqueous media. Org. Biomol. Chem. 2011, 9, 1054–1060, doi:10.1039/c0ob00524j.
[21]
Wu, X.-M.; Gu, Y.-B. TBAF-assisted palladium-catalyzed suzuki reaction in water under the ligand and base-free conditions. Lett. Org. Chem. 2012, 9, 396–400, doi:10.2174/157017812801322408.
[22]
Chanthavong, F.; Leadbeater, N.E. The application of organic bases in microwave-promoted Suzuki coupling reactions in water. Tetrahedron Lett. 2006, 47, 1909–1912, doi:10.1016/j.tetlet.2006.01.092.
[23]
hrngren, P.; Fardost, A.; Russo, F.; Schanche, J.-S.; Fagrell, M.; Larhed, M. Evaluation of a nonresonant microwave applicator for continuous-flow chemistry applications. Org. Process Res. Dev. 2012, 16, 1053–1063, doi:10.1021/op300003b.
[24]
Larhed, M.; Hallberg, A. Microwave-assisted high speed chemistry: A new technique in drug discovery. Drug Discov. Today 2001, 6, 406–416, doi:10.1016/S1359-6446(01)01735-4.
[25]
Kappe, C.O.; Dallinger, D. The impact of microwave synthesis on drug discovery. Nat. Rev. Drug Discov. 2006, 5, 51–63, doi:10.1038/nrd1926.
[26]
Kappe, C.O. Controlled microwave heating in modern organic synthesis. Angew. Chem. Int. Ed. 2004, 43, 6250–6284, doi:10.1002/anie.200400655.
[27]
Avery, K.B.; Devine, W.G.; Kormos, C.M.; Leadbeater, N.E. Use of a silicon carbide multi-well plate in conjunction with microwave heating for rapid ligand synthesis, formation of palladium complexes, and catalyst screening in a Suzuki coupling. Tetrahedron Lett. 2009, 50, 2851–2853, doi:10.1016/j.tetlet.2009.03.140.
[28]
Prokopciva, H.; Ramirez, J.; Fernandez, E.; Kappe, C.O. Microwave-assisted one-pot diboration/Suzuki cross-couplings. A rapid route to tetrasubstituted alkenes. Tetrahedron Lett. 2008, 49, 4831–4835, doi:10.1016/j.tetlet.2008.06.017.
[29]
Glasnov, T.N.; Findenig, S.; Kappe, C.O. Heterogeneous versus homogeneous palladium catalysts for ligandless Mizoroki-Heck reactions: A comparison of batch/microwave and continuous-flow processing. Chem. Eur. J. 2009, 15, 1001–1010, doi:10.1002/chem.200802200.
[30]
Leadbeater, N.E.; Marco, M. Ligand-free palladium catalysis of the Suzuki reaction in water using microwave heating. Org. Lett. 2002, 4, 2973–2976, doi:10.1021/ol0263907.
[31]
Arvela, R.K.; Leadbeater, N.E. Suzuki coupling of aryl chlorides with phenylboronic acid in water, using microwave heating with simultaneous cooling. Org. Lett. 2005, 7, 2101–2104, doi:10.1021/ol0503384.
[32]
Appukkuttan, P.; van der Eycken, E. Recent developments in microwave-assisted, transition-metal-catalysed C–C and C–N bond-forming reactions. Eur. J. Org. Chem. 2008, 2008, 1133–1155, doi:10.1002/ejoc.200701056.
[33]
Dawood, K.M. Microwave-assisted Suzuki-Miyaura and Heck-Mizoroki cross-coupling reactions of aryl chlorides and bromides in water using stable benzothiazole-based palladium(II) precatalysts. Tetrahedron 2007, 63, 9642–9651, doi:10.1016/j.tet.2007.07.029.
[34]
Larhed, M.; Hallberg, A. Microwave-promoted palladium-catalyzed coupling reactions. J. Org. Chem. 1996, 61, 9582–9584, doi:10.1021/jo9612990.
[35]
Nilsson, P.; Ofsson, K.; Larhed, M. Microwave-assisted and metal-catalyzed coupling reactions. Top. Curr. Chem. 2006, 266, 103–144, doi:10.1007/128_046.
[36]
Y？lmaz, ü.; ？ireci, N.; Deniz, S.; Kü？ükbay, H. Synthesis and microwave-assisted catalytic activity of novel bis-benzimidazole salts bearing furfuryl and thenyl moieties in Heck and Suzuki cross-coupling reactions. Appl. Organomet. Chem. 2010, 24, 414–420.
[37]
Kü？ükbay, H.; ？ireci, N.; Y？lmaz, ü.; Akkurt, M.; Yal？？n, ？.P.; Tahir, M.N.; Ott, H. Synthesis, characterization and microwave-assisted catalytic activity of novel benzimidazole salts bearing piperidine and morpholine moieties in Heck cross-coupling reactions. Appl. Organomet. Chem. 2011, 25, 255–261.
[38]
Y？lmaz, ü.; Kü？ükbay, H.; ？ireci, N.; Akkurt, M.; Günal, S.; Durmaz, R.; Tahir, M.N. Synthesis, microwave-promoted catalytic activity in Suzuki-Miyaura cross-coupling reactions and antimicrobial properties of novel benzimidazole salts bearing trimethylsilyl group. Appl. Organomet. Chem. 2011, 25, 366–373.
[39]
？ireci, N.; Y？lmaz, ü.; Kü？ükbay, H. Microwave assisted catalytic activity of some bis-5(6)-nitrobenzimidazole salts for Heck and Suzuki cross-coupling reactions. Asian J. Chem. 2010, 22, 7153–7158.
[40]
Kü？ükbay, H.; ？ireci, N.; Y？lmaz, ü.; Deniz, S.; Akkurt, M.; Bakt？r, Z.; Büyükgüng？r, O. Synthesis, characterization, and microwave-promoted catalytic activity of novel benzimidazole salts bearing silicon-containing substituents in Heck-Mizoroki and Suzuki-Miyaura cross-coupling reactions under aerobic conditions. Turk. J. Chem. 2012, 36, 201–217.
[41]
Phillips, M.A. The formation of 2-substituted benzimidazoles. J. Chem. Soc. 1928, 13, 2393–2399, doi:10.1039/jr9280002393.
[42]
？ireci, N.; Y？lmaz, ü.; Kü？ükbay, H.; Akkurt, M.; Bakt？r, Z.; Türktekin, S.; Büyükgüng？r, O. Synthesis of 1-substituted benzimidazole metal complexes and structural characterization of dichlorobis(1-phenyl-1H-benzimidazole-κN3)cobalt(II) and dichlorobis(1-phenyl-1H-benzimidazole-κN3)zinc(II). J. Coord. Chem. 2011, 64, 1894–1902, doi:10.1080/00958972.2011.584620.
[43]
？etinkaya, E.; Hitchcock, P.B.; Kü？ükbay, H.; Lappert, M.F.; Al-Juaid, S. XXIV*. Preparation of two enetetramine-derived carbenerhodium(I) chloride complexes RhCl(LR)3 and [RhCl(COD)LR]{LR=CN(Me)((CH)4CNMe-o} and the preparation and X-ray structures of the enetetramine L2R and its salt [L2R][BF4]2. J. Organomet. Chem. 1994, 481, 89–95.
[44]
？etinkaya, B.; ？etinkaya, E.; Chamizo, J.A.; Hitchcock, P.B.; Jasim, H.A.; Kü？ükbay, H.; Lappert, M.F. Synthesis and structures of 1,3,1',3'-tetrabenzyl-2,2'-biimidazolidinylidenes (electron-rich alkenes), their aminal intermediates and their degradation products. J. Chem. Soc. Perkin. Trans. 1 1998, 1998, 2047–2054.
[45]
Y？lmaz, ü.; Kü？ükbay, H. Synthis and properties of new endotricyclic electron-rich olefins and their some derivatives. Asian J. Chem. 2009, 21, 6149–6155.
[46]
Rosa, G.R.; Rosa, D.S. NCP pincer palladacycle as a phosphine-free catalyst precursor for the Heck-Mizoroki coupling of aryl halides. RSC Adv. 2012, 2, 5080–5083, doi:10.1039/c2ra01261h.
[47]
Higgs, G. Novel treatments for asthma. Chem. Ind. 1997, 827–830.
[48]
De Vries, J.G. The Heck reaction in the production of fine chemicals. Can. J. Chem. 2001, 79, 1086–1092, doi:10.1139/v01-033.
[49]
Tang, S.; Li, S.-H.; Yan, W.-B. Palladium-catalyzed cross-coupling reaction of aryl(trialkyl)silanes with aryl nitrile. Tetrahedron Lett. 2012, 53, 6743–6746, doi:10.1016/j.tetlet.2012.09.072.
[50]
Nolan, S.P. N-Heterocyclic Carbenes in Synthesis; Wiley-VCH: Weinheim, Germany, 2006; pp. 55–70.
[51]
Huang, W.; Guo, J.; Xiao, Y.; Zhu, M.; Zou, G.; Tang, J. Palladium-benzimidazolium salt catalyst systems for Suzuki coupling: Development of a practical and highly active palladium catalyst system for coupling of aromatic halides with arylboronic acids. Tetrahedron 2005, 61, 9783–9790, doi:10.1016/j.tet.2005.06.060.
Singh, R.; Viciu, M.S.; Kramareva, N.; Navarro, O.; Nolan, S.P. Simple (imidazol-2-ylidene)-Pd-acetate complexes as effective precatalysts for sterically hindered Suzuki-Miyaura couplings. Org. Lett. 2005, 7, 1829–1832.
[54]
Li, H.Y.; Cai, C. A novel system for the Suzuki cross-coupling reaction catalyzed with light fluorous palladium-NHC-complex. J. Fluorine Chem. 2012, 144, 143–146, doi:10.1016/j.jfluchem.2012.08.005.
Durap, F.; Metin, ？.; Aydemir, M.; ？zkar, S. New route to synthesis of PVP-stabilized palladium(0) nanoclusters and their enhanced catalytic activity in Heck and Suzuki cross-coupling reactions. Appl. Organomet. Chem. 2009, 23, 498–503.
[58]
Akba, O.; Durap, F.; Aydemir, M.; Baysal, A.; Gümgüm, B.; ？zkar, S. Synthesis and characterizations of N,N,N',N'-tetrakis (diphenylphosphino)ethylendiamine derivatives: Use of palladium(II) complex as pre-catalyst in Suzuki coupling and Heck reactions. J. Organomet. Chem. 2009, 694, 731–736.
[59]
Xi, C.; Wu, Y.; Yan, X. cis-Fashioned palladium (II) complexes of 2-phenylbenzimidazole ligands: Synthesis, characterization, and catalytic behavior towards Suzuki-Miyaura reaction. J. Organomet. Chem. 2008, 693, 3842–3846, doi:10.1016/j.jorganchem.2008.09.042.
