Synthesis, Structural Characterization, Catalytic Activity on Suzuki-Miyaura and Mizoroki-Heck Coupling Reaction of Dichloro[1-(2-metil-2-propenil)-3-(3,4,5- trimethoxybenzyl) benzimidazole-2-ylidene] pyridine palladium(II) Complex

Öz

N-heterocyclic carbene-metal complexes exhibit high activity as catalysts. Synthesis of new catalysts and their use in organic synthesis reactions is one of the most important work areas of coordination chemistry. In this study, with the goal of achieving highly efficient palladium catalyzed cross-coupling reactions under mild reaction conditions, 1-(2-metil-2-propenil-3-(3,4,5-
trimethoxybenzyl)benzimidazoliumchloride salt (1) and its Pd(II)-N-heterocyclic carbene complex (2) were synthesized. Structures of obtained both compounds characterized by elemental analysis, FT-IR, 1H NMR and 13C NMR spectroscopies. Afterward, Pd(II)-NHC (2) complex was investigated catalytic activities on SuzukiMiyaura and Mizoroki-Heck coupling reactions. It was observed that synthesized dichloro[1-(2-metil-2-propenil)-3-(3,4,5-trimethoxybenzyl)benzimidazole-2- ylidene]pyridine palladium(II) complex exhibited quite high activity on SuzukiMiyaura coupling reaction at water/isopropyl alcohol mixture

Anahtar Kelimeler

• N-heterocyclic carbene
• Palladium
• Suzuki-Miyaura
• Mizoroki-Heck

Dikloro [1-(2-metil-2-propenil)-3-(3,4,5-trimetoksibenzil) benzimidazol-2-iliden] piridin paladyum(II) Kompleksinin Sentezi, Yapısal Karakterizasyonu, Suzuki-Miyaura ve Mizoroki-Heck Eşleşme Tepkimelerindeki Katalitik Aktivitesi

Öz

N-heterosiklik karben-metal kompleksleri katalizör olarak yüksek aktivite göstermektedirler. Yeni katalizörlerin sentezlenmesi ve organik sentez tepkimelerinde kullanılması koordinasyon kimyasının en önemli çalışma alanlarından biridir. Bu çalışmada, ılımlı tepkime koşulları altında, yüksek verimli paladyum katalizli eşleşme tepkimelerini gerçekleştirmek amacıyla, 1-(2-metil-2-propenil)-3-(3,4,5-trimetoksibenzil)benzimidazolyum klorür tuzu (1)  ve bu yeni tuzdan Pd(II)-N-heterosiklik karben kompleksi (NHC) (2) sentezlendi. Elde edilen her iki bileşiğin yapısı elementel analiz, FT-IR, ¹H NMR ve ¹³C NMR spektroskopileri ile karakterize edildi. Daha sonra Pd(II)-NHC (2) kompleksinin Suzuki-Miyaura ve Mizoroki-Heck eşleşme tepkimelerindeki katalitik aktivitesi incelendi. Sentezlenen dikloro[1-(2-metil-2-propenil)-3-(3,4,5-trimetoksibenzil) benzimidazol-2-iliden] piridin paladyum(II) kompleksinin Suzuki-Miyaura eşleşme tepkimesi için su-izopropil alkol karışımında oldukça yüksek aktivite gösterdiği gözlendi.

Anahtar Kelimeler

• N-heterosiklik karben
• Paladyum
• Suzuki-Miyaura
• Mizoroki-Heck

Kaynakça

1. [1] Díez-González, S., Marion, N., Nolan, S. P. 2009. N-heterocyclic carbenes in late transition metal catalysis. Chemical Reviews, 109(8), 3612-3676.
2. [2] Irikura, K., Goddard III K, W. A., Beauchamp, J. L. 1992. Singlet-triplet gaps in substituted carbenes CXY (X, Y= H, fluoro, chloro, bromo, iodo, silyl). Journal of the American Chemical Society, 114(1), 48-51.
3. [3] Feller, D., Borden, W. T., Davidson, E. R. 1980. Dependence of the singlet-triplet splitting in heterosubstituted carbenes on the heteroatom electronegativity and conformation. Chemical Physics Letters, 71(1), 22-26.
4. [4] Arduengo III, A. J., Harlow, R. L., Kline, M. 1991. A stable crystalline carbene [Erratum to document cited in CA114 (7): 62009r]. Journal of the American Chemical Society, 113(7), 2801-2801.
5. [5] Wanzlick, H. W., Schönherr, H. J. 1968. Direct synthesis of a mercury salt‐carbene complex. Angewandte Chemie International Edition, 7(2), 141-142.
6. [6] Öfele, K. 1968. 1, 3-Dimethyl-4-imidazolinyliden -(2)-pentacarbonylchrom ein neuer Übergangs metall-carben-komplex. Journal of Organometal lic Chemistry, 12(3), P42-P43.
7. [7] Kuhl, S., Schneider, R., Fort, Y. 2003. Transfer hydrogenation of imines catalyzed by a nickel (0)/NHC complex. Organometallics, 22(21), 4184-4186.
8. [8] Bortenschlager, M., Schütz, J., von Preysing, D., Nuyken, O., Herrmann, W. A., Weberskirch, R. 2005. Rhodium–NHC-complexes as potent catalysts in the hydroformylation of 1-octene. Journal of organometallic chemistry, 690(24), 6233-6237.

9. [9] Boubakri, L., Yasar, S., Dorcet, V., Roisnel, T., Bruneau, C., Hamdi, N., Ozdemir, I. 2017. Synthesis and catalytic applications of palladium N-heterocyclic carbene complexes as efficient pre-catalysts for Suzuki–Miyaura and Sonogashira coupling reactions. New Journal of Chemistry, 41(12), 5105-5113.
10. [10] Rouen, M., Queval, P., Falivene, L., Allard, J., Toupet, L., Crévisy, C., Mauduit, M. 2014. Cationic Bis‐N‐Heterocyclic Carbene (NHC) Ruthenium Complex: Structure and Application as Latent Catalyst in Olefin Metathesis. Chemistry-A European Journal, 20(42), 13716-13721.
11. [11] Berthon-Gelloz, G., Buisine, O., Brière, J. F., Michaud, G., Stérin, S., Mignani, G., Markó, I. E. 2005. Synthetic and structural studies of NHC–Pt (dvtms) complexes and their application as alkene hydrosilylation catalysts (NHC= N-heterocyclic carbene, dvtms= divinyltetramethylsiloxane). Journal of Organometallic Chemistry, 690(24), 6156-6168.
12. [12] Lazaro, G., Iglesias, M., Fernández‐Alvarez, F. J., Miguel, S., Pablo, J., Pérez‐Torrente, J. J., Oro, L. A. 2013. Synthesis of poly (silyl ether) s by Rhodium (I)–NHC catalyzed hydrosilylation: Homogeneous versus heterogeneous catalysis. ChemCatChem, 5(5), 1133-1141.
13. [13] Kantchev, E.A.B., Brian, C.J.O., Organ, M.G. 2006. Pd-N-heterocyclic carbene (NHC) catalysts for cross-coupling reactions. Aldrichimica Acta 39, 97–111.
14. [14] Sharif, S., Rucker, R. P., Chandrasoma, N., Mitchell, D., Rodriguez, M. J., Froese, R. D., Organ, M. G. 2015. Selective Monoarylation of Primary Amines Using the Pd‐PEPPSI‐IPentCl Precatalyst. Angewandte Chemie International Edition, 54(33), 9507-9511.
15. [15] Suzuki, A. 1999. Recent advances in the cross-coupling reactions of organoboron derivatives with organic electrophiles. Journal of Organometallic Chemistry, 576(1), 147-168.
16. [16] 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(36), 3437-3440.
17. [17] Han, F. S. 2013. Transition-metal-catalyzed Suzuki–Miyaura cross-coupling reactions: a remarkable advance from palladium to nickel catalysts. Chemical Society Reviews, 42(12), 5270-5298.
18. [18] Bringmann, G., Gulder, T., Gulder, T. A., Breuning, M. 2010. Atroposelective total synthesis of axially chiral biaryl natural products. Chemical reviews, 111(2), 563-639.
19. [19] Alberico, D., Scott, M. E., Lautens, M. 2007. Aryl− aryl bond formation by transition-metal-catalyzed direct arylation. Chemical reviews, 107(1), 174-238.
20. [20] Narayan, S., Muldoon, J., Finn, M. G., Fokin, V. V., Kolb, H. C., Sharpless, K. B. 2005. “On water”: Unique reactivity of organic compounds in aqueous suspension. Angewandte Chemie International Edition, 44(21), 3275-3279.
21. [21] Butler, R. N., Coyne, A. G. 2010. Water: Nature’s Reaction Enforcer Comparative Effects for Organic Synthesis “In-Water” and “On-Water”. Chemical reviews, 110(10), 6302-6337
22. [22] Organ, M. G., Avola, S., Dubovyk, I., Hadei, N., Kantchev, E. A. B., O'Brien, C. J., Valente, C. 2006. A User‐Friendly, All‐Purpose Pd–NHC (NHC= N‐Heterocyclic Carbene) Precatalyst for the Negishi Reaction: A Step Towards a Universal Cross‐Coupling Catalyst. Chemistry-A European Journal, 12(18), 4749-4755.
23. [23] O'Brien, C. J., Kantchev, E. A. B., Valente, C., Hadei, N., Chass, G. A., Lough, A., Organ, M. G. 2006. Easily Prepared Air‐and Moisture‐Stable Pd–NHC (NHC= N‐Heterocyclic Carbene) Complexes: A Reliable, User‐Friendly, Highly Active Palladium Precatalyst for the Suzuki–Miyaura Reaction. Chemistry-a European Journal, 12(18), 4743-4748.
24. [24] Doǧan, Ö., Demir, S., Özdemir, İ., Cetinkaya, B. 2011. Palladium (II) NHC complexes containing benzimidazole ligand as a catalyst for C-N bond formation. Applied Organometallic Chemistry, 25(3), 163-167.