Yeni Palladyum-N-Heterosiklik Karben Komplekslerinin Sentezi ve Mono-Florobenzenlerin Direkt Arilasyonundaki Katalitik Uygulamaları

Year 2019, , 933 - 943, 01.06.2019

Murat Kaloğlu

https://doi.org/10.21597/jist.482668

Abstract

Bu çalışmada, N-heterosiklik karben (NHC) ligandı içeren yeni palladyum kompleksleri

sentezlendi ve yapıları 1H NMR, 13C NMR ve element analizi yöntemleri ile karakterize edildi.

Palladyum-NHC komplekslerinin katalitik aktivitesi, mono-florobenzenlerin çeşitli aril bromürler ile

direkt arilasyonu tepkimelerinde test edildi. Palladyum-NHC kompleksleri, elektron verici ve elektron

çekici aril bromürler için yüksek katalitik aktivite gösterdi.

Keywords

N-Heterosiklik karben, palladyum, direkt arilasyon, florobenzen

Synthesis of Novel Palladium-N-Heterocyclic Carbene Complexes and Their Catalytic Application in the Direct Arylation of Mono-Fluorobenzenes

Abstract

In this study, novel palladium complexes containing N-heterocyclic carbene (NHC)

ligands were synthesized and their structures characterized by 1H NMR, 13C NMR and elemental

analysis techniques. The catalytic activities of palladium-NHC complexes were tested in the direct

arylation reactions of mono-fluorobenzenes with various aryl bromides. Palladium-NHC complexes

showed the high catalytic activity for electron-donating and electron-drawing aryl bromides.

Keywords

N-Heterocyclic carbene, palladium, direct arylation, fluorobenzene

References

• Ackermann L, Vicente R, Kapdi AR, 2009. Transition‐Metal‐Catalyzed Direct Arylation of (Hetero)Arenes by C-H Bond Cleavage. Angewandte Chemie International Edition, 48 (52): 9792-9826.
• Arroniz C, Ironmonger A, Rassias G, Larrosa I, 2013. Direct ortho-Arylation of ortho-Substituted Benzoic Acids: Overriding Pd-Catalyzed Protodecarboxylation. Organic Letters, 15 (4): 910-913.
• Bourissou D, Guerret O, Gabbai FP, Bertrand G, 2000. Stable Carbenes. Chemical Reviews, 100 (1): 39-92.
• Chen F, Min Q-Q, Zhang X, 2012. Pd-Catalyzed Direct Arylation of Polyfluoroarenes on Water under Mild Conditions Using PPh3 Ligand. The Journal of Organic Chemistry, 77 (6): 2992-2998.
• Chiong HA, Pham Q-N, Daugulis O, 2007. Two Methods for Direct ortho-Arylation of Benzoic Acids. Journal of American Chemical Society, 129 (32): 9879-9884.
• Cornella J, Righi M, Larrosa I, 2011. Carboxylic Acids as Traceless Directing Groups for Formal meta‐Selective Direct Arylation. Angewandte Chemie International Edition, 50 (40): 9429-9432.
• Glorius F, 2007. Topics in Organometallic Chemistry Vol. 21: N-Heterocyclic Carbenes in Transition Metal Catalysis. Springer, Heidelberg-Germany.
• Groult H, Leroux FR, Tressaud A, 2017. Modern Synthesis Processes and Reactivity of Fluorinated Compounds. Elsevier Inc., London-England.
• Hahn FE, 2006. Heterocyclic Carbenes. Angewandte Chemie International Edition, 45 (9): 1348-1352.
• Johansson Seechurn CCC, Kitching MO, Colacot TJ, Snieckus V, 2012. Palladium‐Catalyzed Cross‐Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize. Angewandte Chemie International Edition, 51 (21): 5062-5085.
• Kaloğlu M, Kaloğlu N, Özdemir İ, 2018. Direct C-H Bond Activation of Benzoxazole and Benzothiazole with Aryl Bromides Catalyzed by Palladium(II)-N-Heterocyclic Carbene Complexes. Chinese Journal of Chemistry, 36: 837-844.
• Kaloğlu M, Kaloğlu N, Özdemir İ, 2018. Direct C-H Bond Arylation of C2-Blocked Pyrrole with Aryl Halides Using Palladium(II)-N-Heterocyclic Carbene Catalysts. ChemistrySelect, 3, 5600-5607.
• Kaloğlu M, Kaloğlu N, Özdemir İ, Günal S, Özdemir İ, 2016. Novel Benzimidazol-2-ylidene Carbene Precursors and Their Silver(I) Complexes: Potential Antimicrobial Agents. Bioorganic & Medicinal Chemistry, 24: 3649-3656.
• Kaloğlu M, Özdemir İ, 2018. Palladium(II)-N-Heterocyclic Carbene Complexes: Efficient Catalysts for the Direct C-H Bond Arylation of Furans with Aryl Halides. Applied Organometallic Chemistry, 32: e4399.
• Kaloğlu M, Özdemir İ, 2018. Palladium(II)-N-heterocyclic carbene-catalyzed direct C2- or C5-arylation of thiazoles with aryl bromides. Tetrahedron, 74: 2837-2845.
• Lafrance M, Rowley CN, Woo TK, Fagnou K, 2006. Catalytic Intermolecular Direct Arylation of Perfluorobenzenes. Journal of American Chemical Society, 128 (27): 8754-8756.
• Lafrance M, Shore D, Fagnou K, 2006. Mild and General Conditions for the Cross-Coupling of Aryl Halides with Pentafluorobenzene and Other Perfluoroaromatics. Organic Letters, 8 (22): 5097-5100.
• Lapointe D, Markiewicz T, Whipp CJ, Toderian A, Fagnou A, J. 2011. Predictable and Site-Selective Functionalization of Poly(hetero)arene Compounds by Palladium Catalysis. The Journal of Organic Chemistry, 76 (3): 749-759.
• Lentijo S, Aullon G, Miguel JA, Espinet P, 2013. Highly Fluorescent Complexes with Gold, Palladium or Platinum Linked to Perylene Through a Tetrafluorophenyl Group. Dalton Transactions, 42: 6353-6365.
• Li H, Sun C-L, Yu M, Yu D-G, Li B-J, Shi Z-J, 2011. The Catalytic Ability of Various Transition Metals in the Direct Functionalization of Aromatic C-H Bonds. Chemistry A European Journal, 17 (13): 3593-3597.
• Li JJ, Gribble GW, 2000. Palladium in Heterocyclic Chemistry. Pergamon, Amsterdam-Holland.
• Negishi E, 2002. Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley-Interscience, New York-USA.
• Nolan SP, 2014. N-Heterocyclic Carbenes: Effective Tools for Organometallic Synthesis. Wiley-VCH, Weinheim, Germany.
• Özdemir İ, Gök Y, Özeroğlu Ö, Kaloğlu M, Doucet H, Bruneau C, 2010. N‐Heterocyclic Carbenes: Useful Ligands for the Palladium‐Catalysed Direct C5 Arylation of Heteroaromatics with Aryl Bromides or Electron‐Deficient Aryl Chlorides. European Journal of Inorganic Chemistry, 12: 1798-1805.
• Rene O, Fagnou K, 2010. Room-Temperature Direct Arylation of Polyfluorinated Arenes under Biphasic Conditions. Organic Letters, 12 (9): 2116-2119.
• Ricci P, Krämer K, Cambeiro XC, Larrosa I, 2013. Arene-Metal π-Complexation as a Traceless Reactivity Enhancer for C-H Arylation. Journal of American Chemical Society, 135 (36): 13258-13261.
• Wang Y-N, Guo X-Q, Zhu X-H, Zhong R, Cai L-H, Hou X-F, 2012. Pd(OAc)2 Catalyzed Direct Arylation of Electron-Deficient Arenes Without Ligands or with Monoprotected Amino Acid Assistance. Chemical Communication, 48: 10437-10439.
• Yan T, Zhao L, He M, Soule J-F, Bruneau C, Doucet H, 2014. Reactivity of 3‐Substituted Fluorobenzenes in Palladium‐Catalysed Direct Arylations with Aryl Bromides. Advanced Synthesis and Catalysis, 356 (7): 1586-1596.