Ülkü YILMAZ, Hasan KÜÇÜKBAY, Sevim TÜRKTEKİN ÇELİKESİR

Synthesis of novel benzimidazole salts and microwave-assisted catalytic activity of in situ generated Pd nanoparticles from a catalyst system consisting of benzimidazol salt, Pd(OAc)2, and base in a Suzuki-Miyaura reaction

Novel benzimidazolium salts having N-benzyl or N-(4-substitutedbenzyl) groups were synthesized and their microwave-promoted catalytic activity for the Suzuki--Miyaura cross-coupling reaction were determined using in situ formed palladium(0) nanoparticles (PdNPs) from a catalytic system consisting of Pd(OAc)2/K2CO3 in DMF/H2O. PdNPs were characterized by X-ray diffraction (XRD) pattern and particle size of in situ generated PdNPs from the Pd(111) plane was determined to be of diameter 19.6 nm by the Debye--Scherrer equation. Moreover, the yield of the Suzuki--Miyaura reactions with aryl iodides and aryl bromides was found to be nearly quantitative. The synthesized benzimidazole salts (1--5) were identified by 1H and 13C NMR and IR spectroscopic methods, and micro analysis. The molecular structure of 5 was also determined by X-ray crystallography.

Anahtar Kelimeler:

Benzimidazole salt, N-heterocyclic carbenes, palladium nanoparticles, cross-coupling reaction, Suzuki--Miyaura coupling, microwave

Synthesis of novel benzimidazole salts and microwave-assisted catalytic activity of in situ generated Pd nanoparticles from a catalyst system consisting of benzimidazol salt, Pd(OAc) 2 , and base in a Suzuki-Miyaura reaction

Keywords:

Benzimidazole salt, N-heterocyclic carbenes, palladium nanoparticles, cross-coupling reaction, Suzuki--Miyaura coupling, microwave,

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Suzuki, A. Pure Appl. Chem. 1985, 57, 1749–1758.
Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457–2483.
Yan, J.; Zhou, Z.; Zhu, M. Tetrahedron Lett. 2005, 46, 8173–8175.
Alonso, F.; Beletskaya, I. P.; Yus, M. Tetrahedron 2008, 64, 3047–3101.
Yin, L.; Liebscher, J. Chem. Rev. 2007, 107, 133–173.
Tudose, A.; Delaude, L.; Andre, B.; Demonceau, A. Tetrahedron Lett. 2006, 47, 8529–8533.
Ackermann, L.; Vicente, R.; Kapdi, A. R. Angew. Chem. Int. Ed. 2009, 48, 9792–9826.
Kantchev, E. A. B.; O’Brien, C. J.; Organ, M. G. Angew. Chem. Int. Ed. 2007, 46, 2768–2813.
Suzuki, A. ChemComm. 2005, 4759–4763.
Hajipour, A. R.; Karami, K.; Tavakoli, G. Appl. Organomet. Chem. 2011, 25, 567–576. Dawood, K. M. Tetrahedron 2007, 63, 9642–9651.
Linninger, C. S.; Herdtweck, E.; Hoffmann, S. D.; Herrmann, W. A. J. Mol. Struct. 2008, 890, 192–197.
Singh, R.; Viciu, M. S.; Kramareva, N.; Navarro, O.; Nolan, S. P. Org. Lett. 2005, 7, 1829–1832.
Marion, N.; Nolan, S. P. Acc. Chem. Res. 2008, 41, 1440–1449.
Hahn, F. E.; Jahnke, M. C.; Pape, T. Organometallics 2006, 25, 5927–5936.
Durap, F.; Metin, ¨ O.; Aydemir, M.; ¨ Ozkar, S. Appl. Organomet. Chem. 2009, 24, 498–503.
G¨ ok, Y.; G¨ urb¨ uz, N.; ¨ Ozdemir, ˙I.; C ¸ etinkaya, B.; C ¸ etinkaya, E. Appl. Organomet. Chem. 2005; 19, 870–874.
S ¸ireci, N.; Yılmaz, ¨ U.; K¨ u¸ c¨ ukbay, H. Asian J. Chem. 2010, 22, 7153–7158.
Chanthavong, F.; Leadbeater, N. E. Tetrahedron Lett. 2006, 47, 1909–1912.
Kappe, C. O.; Angew. Chem. Int. Ed. 2004, 43, 6250–6284.
Hahn, F. E.; Jahnke, M. C. Angew. Chem. Int. Ed. 2008, 47, 3122–3172.
K¨ u¸ c¨ ukbay, H.; C ¸ etinkaya, B.; Guesmi, S.; Dixneuf, P. H. Organometallics 1996, 5, 2434–2439.
Mercan, D.; C ¸ etinkaya, E.; C ¸ etinkaya, B. J. Organomet. Chem. 2011, 696, 1359–1366.
Nolan, S. P. N-Heterocyclic Carbenes in Synthesis, Wiley-VCH: Weinheim, 2006.
¨ Ozdemir, ˙I.; Demir, S.; Ya¸sar, S.; C ¸ etinkaya, B. Appl. Organomet. Chem. 2005, 19, 55–58.
Loupy, A. Microwaves in Organic Synthesis, 2nd ed., Wiley-VCH: Weinheim, 2006.
Prokopvova, H.; Ramirez, J.; Fernandez, E.; Kappe, C. O. Tetrahedron Lett. 2008, 49, 4831–4835.
Glasnov, T. N.; Findenig, S.; Kappe, C.O. Chem. Eur. J. 2009, 15, 1001–1010.
Leadbeater, N. E.; Marco, M. Org. Lett. 2002, 4, 2973–2976.
Avery, K. B.; Devine, W. G.; Kormos, C. M.; Leadbeater, N. E. Tetrahedron Lett. 2009, 50, 2851–2853.
Arvela, R. K.; Leadbeater, N. E. Org. Lett. 2005, 7, 2101–2104.
Trejos, A.; Fardost, A.; Yahiaoui, S.; Larhed, M. Chem. Commun. 2009, 7587–7589.
Lindh, J.; Enquist, P-A.; Pilotti, ˚ A.; Nilsson, P.; Larhed, M. J. Org. Chem. 2007, 72, 7957–7962.
Zhou, Z-G.; Shi, J-C.; Hu, Q-S.; Xie, Y-R.; Du, Z-Y.; Zhang, S-Y. Appl. Organomet. Chem. 2011, 25, 616–619. Singh, B. K.; Kaval, N.; Tomar, S.; Van der Eycken, E.; Parmar, V. S. Org. Process Res. Dev. 2008, 12, 468–474. Appukkuttan, P.; Van der Eycken, E. Eur. J. Org. Chem. 2008, 1133–1155.
Yılmaz, ¨ U.; S ¸ireci, N.; Deniz, S.; K¨ u¸ c¨ ukbay, H. Appl. Organomet. Chem. 2010, 24, 414–420.
Yılmaz, ¨ U.; K¨ u¸ c¨ ukbay, H.; S ¸ireci, N.; Akkurt, M.; G¨ unal, S.; Durmaz, R.; Tahir, M. N. Appl. Organomet. Chem. 2011, 25, 366–373.
Balanta, A.; Godard, C.; Claver, C. Chem. Soc. Rev. 2011, 40, 4973–4985.
Reetz, M. T.; Breinbauer, R.; Wanninger, K. Tetrahedron Lett. 1996, 37, 4499–4502.
Astruc, D. Inorg. Chem. 2007, 46, 1884–1894.
Sawoo, S.; Srimani, D.; Dutta, P.; Lahiri, R.; Sarkar, A. Tetrahedron, 2009, 65, 4367–4374.
Mao, P.; Yang, L.; Xiao, Y.; Yuan, J.; Liu, X.; Song, M. J. Organomet. Chem. 2012, 705, 39–43.
Zawartka, W.; Gniewek, A.; Trzeciak, A. M.; Ziolkowsski, J. J.; Pernak, J. J. Mol. Catal. A: Chem. 2009, 304, 8–
Borkowski, T.; Trzeciak, A. M.; Bukowski, W.; Bukowska, A.; Tylus, W.; Kepinski, L. Appl. Catal. A: Gen. 2010, 378, 83–89.
Metin, ¨ O.; Durap, F.; Aydemir, M.; ¨ Ozkar, S. J. Mol. Catal. A: Chem. 2011, 337, 39–44.
Li, Y.; Hong, X. M.; Collard, D. M.; El-Sayed, M. A. Org. Lett. 2000, 2, 2385–2388. Ellis, P. J.; Fairlamb, I. J. A.; Hackett, S. F. J.; Wilson, K.; Lee, A. F. Angew. Chem. Int. Ed. 2010, 49, 1820–1824. Martins, D. L.; Alvarez, H. M.; Aguiar, L. C. S. Tetrahedron Lett. 2010, 51, 6814–6817.
Yu, Y.; Hu, T.; Chen, X.; Xu, K.; Zhang, J.; Huang, J. Chem. Commun. 2011, 47, 3592–3594.
Magdesieva, T. V.; Nikitin, O. M.; Levitsky, O. A.; Zinovyeva, V. A.; Bezverkhyy, I.; Zolotukhina, E. V.; Vorotyntsev, M. A. J. Mol. Catal. A. 2012, 353–354, 50–57.
Akkurt, M.; Yıldırım, ¨ O. S.; S ¸ireci, N.; K¨ u¸ c¨ ukbay, H.; B¨ uy¨ ukg¨ ung¨ or, O. Acta Cryst. 2008, E64, o2136–o2137.
Pozharskii, A. F.; Simanov, A. M. J. Gen. Chem. USSR, 1963, 33, 172.
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.
Altomare, A.; Burla, M.C.; Camalli, M.; Cascarano, G.L.; Giacovazzo, C.; Guagliardi, A.; Moliterni, A.G.G.; Polidori, G.; Spagna, R. J. Appl. Cryst. 1999, 32, 339–340.
Sheldrick, G. M. Acta Cryst. 2008, A64, 112–122.
Farrugia, L. J. J. Appl. Cryst. 1997, 30, 565–566.
¨ Ozdemir, ˙I.; S ¸ahin, N.; G¨ ok, Y.; Demir, S.; C ¸ etinkaya, B. J. Mol. Catal. A. 2005, 234, 181–185.
Huang, W.; Guo, E. P.; Xiao, Y. J.; Zhu, M. F.; Zou, G.; Tang, J. Tetrahedron 2005, 61, 9783–790.
Illa, O.; Rodriguez-Garcia, C.; Acosta-Silva, C.; Favier, I.; Picurelli, D.; Oliva, A.; Gomez, M.; Branchadell, V.; Ortuno, R. M. Organometallics 2007, 26, 3306–3314.
Sun, Z.; Cheng, F.; Dai, X. J. Autom Method. Manag. 2009, Art. ID 496281, doi: 10.1155/2009/496281, 1–5.
T¨ urktekin, S.; Akkurt, M.; Orhan, E.; K¨ u¸ c¨ ukbay, F. Z.; K¨ u¸ c¨ ukbay, H.; B¨ uy¨ ukg¨ ung¨ or, O. Acta Cryst. 2004, E60, m1220–m1222.
Akkurt, M.; ¨ Ozt¨ urk, S.; S ¸ireci, N.; K¨ u¸ c¨ ukbay, H.; B¨ uy¨ ukg¨ ung¨ or, O. Acta Cryst. 2004, E60, o1185–o1187.