Pirolidinin Alkollerle Rutenyum-NHC Katalizli N-Alkilasyonu

Yıl 2025, Cilt: 29 Sayı: 3, 528 - 537, 25.12.2025

Nazan Kaloğlu

https://doi.org/10.19113/sdufenbed.1607703

Öz

Bu çalışmada, N-heterosiklik karben (NHC) ligandı içeren, [RuCl2(η6-p-simen) (NHC)] genel formülüne sahip yarı sandviç tipi iki yeni rutenyum-NHC kompleksi sentezlendi. Sentezlenen komplekslerin yapıları spektroskopik ve analitik yöntemlerle karakterize edildi. Rutenyum-NHC kompleksleri, pirolidin ve çeşitli alkol türevlerinin hidrojen ödünç alma yöntemiyle N-alkilasyonunda katalizör olarak kullanıldı. Katalitik tepkimeler, %1 mol katalizör yüklemesi varlığında 120 °C'de, 16 saatte ve çözücüsüz tepkime ortamında gerçekleştirildi. Tüm rutenyum-NHC kompleksleri, test edilen koşullar altında oldukça iyi katalitik aktivite gösterdi ve hedeflenen N-alkilpirolidin ürünleri yüksek seçicilikte elde edildi.

Anahtar Kelimeler

Kataliz , Rutenyum , Pirolidin , N-alkilasyon

Ruthenium-NHC Catalysed N-Alkylation of Pyrrolidine with Alcohols

Öz

In this study, two new half-sandwich type ruthenium-NHC complexes with the general formula [RuCl2(η6-p-cymene)(NHC)] containing N-heterocyclic carbene (NHC) ligands were synthesised. The structures of the synthesised complexes were characterised by spectroscopic and analytical methods. The ruthenium-NHC complexes were used as catalysts in the N-alkylation of pyrrolidine and various alcohol derivatives by hydrogen borrowing strategy. The catalytic reactions were carried out in the presence of 1 mol% catalyst loading at 120 °C for 16 h in a solvent-free reaction medium. All ruthenium-NHC complexes showed very good catalytic activity under the tested conditions and the targeted N-alkylpyrrolidine products were obtained with high selectivity.

Anahtar Kelimeler

Catalysis , Ruthenium , Pyrrolidine , N-Alkylation

Kaynakça

• [1] Brown (Ed.), B.R. 2008. Cambridge University, Cambridge. [2] Lawrence (Ed.), S.A. 2006. Cambridge University, Cambridge.
• [3] A. Ricci (Ed.), 2008. Wiley-VCH, Weinheim.
• [4] a) Lawrence (Ed.), S.A. 2004. Cambridge University, Cambridge; b) Brown (Ed.), B.R. 2004. Cambridge University, Cambridge.
• [5] a) Nixon, T. D., Whittlesey, M.K., Williams, J.M.J. 2009. Dalton Transactions. 5, 753–762;
• b) Hamid, M.H.S.A., Slatford, P.A., Williams, J.M.J. 2007. Advanced Synthesis & Catalysis. 349 (10) 1555–1575;
• c) Guillena, G., Ramón, D.J., Yus, M. 2010. Chemical Reviews. 110 (3) 1611–1641;
• d) Guillena, G., Ramón, D.J., Yus, M. 2007. Angewandte Chemie International Edition. 46 (14) 2358–2364.
• [6] a) Shi, F., Cui, X. 2018. Catalytic Amination for N-Alkyl Amine Synthesis, Academic Press, London, 2018. b) Yasmeen, F., Ahmad, M., Aslam, S., Zubair, M., Naqvi, A. R. 2025. Synthetic Communications. https://doi.org/10.1080/00397911.2025.2490575. [7] Lamb, G.W., Williams, J.M.J. 2008. Chimica Oggi. 26, 17–19.
• [8] Grigg, R., Mitchell, T.R.B., Sutthivaiyakitt, S., Tongpenyai, N. 1981. Journal of the Chemical Society Chemical Communications, 12, 611–612.
• [9] Watanabe, Y., Tsuji, Y., Ohsugi, Y. 1981. Tetrahedron Letters. 22 (28) 2667–2670. [10] Murahashi, S. I., Kondo, K., Hakata, T. 1982. Tetrahedron Letters. 23 (38) 229–232.
• [11] a) Zhang, Y., Lim, C.-S., Sim, D.S.B., Pan, H.-J., Zhao, Y. 2014. Angewandte Chemie International Edition. 53 (5) 1399–1403;
• b) Rong, Z. Q. Zhang, Y., Chua, R.H.B., Pan, H. J., Zhao, Y. 2015. Journal of the American Chemical Society. 137 (15) 4944–4947.
• [12] a) Hamid, M.H.S.A., Williams, J.M.J. 2007. Chemical Communications. 7, 725–727;
• b) Hamid, M.H.S.A., Allen, C.L., Lamb, G.W., Maxwell, A.C., Maytum, H.C., Watson, A.J.A., Williams, J.M.J. 2009. Journal of American Chemical Society. 131 (5) 1766–1774;
• c) Blacker, A.J., Farah, M.M., Hall, M.I., Marsden, S.P., Saidi, O., Williams, J.M.J. 2009. Organic Letters. 11 (9) 2039–2042;
• d) Watson, A.J.A., Maxwell, A.C., Williams, J.M.J. 2011. The Journal of Organic Chemistry. 76 (7) 2328–2331.
• [13] a) Imm, S., Bahn, S., Neubert, L., Neumann, H., Beller, M. 2010. Angewandte Chemie International Edition. 49 (48) 8126–8129;
• b) Imm, S. Bahn, S., Zhang, M., Neubert, M., Neumann, H., Klasovsky, F., Pfeffer, J., Haas, T., Beller, M. 2011. Angewandte Chemie International Edition. 50, 7599–7603;
• c) Bahn, S., Imm, S., Mevius, K., Neubert, L., Tillack, A., Williams, J.M.J., Beller, M. 2010. Chemistry A European Journal. 16 (12) 3590–3593.
• [14] a) Gunanathan, C., Milstein, D. 2008. Angewandte Chemie International Edition. 47 (45) 8661–8664.
• b) Gunanathan, C., Milstein, D. 2011. Accounts of Chemical Research. 44 (8) 588–602.
• [15] a) Fujita, K.I., Enoki, Y., Yamaguchi, R. 2008. Tetrahedron 64 (8) 1943–1954;
• b) Kawahara, R., Fujita, K. I., Yamaguchi, R. 2010. Journal of the American Chemical Society. 132 (43) 15108–15111; c) Kawahara, R., Fujita, K. I., Yamaguchi, R. 2011. Advanced Synthesis Catalysis. 353 (7) 1161–1168.
• [16] a) Yang, Q., Wang, Q., Yu, Z. 2015. Chemical Society Reviews. 44 (8) 2305–2329;
• b) Bartoszewicz, A., Marcos, R., Sahoo, S., Inge, A.K., Zou, X., Martín-Matute, B., 2012. Chemistry European Journal. 18 (45) 14510–14519;
• [17] a) Glorius (Ed.), F. 2007. Topics in Organometallic Chemistry: N-Heterocyclic Carbenes in Transition Metal Catalysis, Vol. 21 Springer, Heidelberg. b) Nolan (Ed.), S.P. 2006. N-Heterocyclic Carbenes in Synthesis, Wiley, Weinheim. c) Chakraborty, S., Akkattu, T. B. 2024. Nature Catalysis. (7) 1060-1062. d) Zhou, T., Jarzynska, U.G., Szostak, M. 2024. Coordination Chemistry Reviews. (512)215867.
• [18] Şahin, Z., Gürbüz, N., Özdemir, İ., Şahin, O., Büyükgüngör, O., Achard, M., Bruneau, C. 2015. Organometallics. 34 (11) 2296-2304.
• [19] Kaloğlu, N., Özdemir, İ., Gürbüz, N., Achard, M., Bruneau, C. 2016. Catalysis Communication. 74 (2016) 33-38.
• [20] Kaloğlu, M., Gürbüz, N., Sémeril, D., Özdemir, İ. 2018. European Journal of Inorganic Chemistry. 10. 1236-1243.
• [21] Perrin, D.D., Armarego, W.F.F., Perrin, D.R. 1980. Purification of laboratory chemicals, Pergamon Press Ltd, Sec. Ed.
• [22] Kaloğlu, M. 2019. Inorganica Chimica Acta. 498, 119163.
• [23] Kaloğlu, M., Özdemir, İ. 2018. Applied Organometallic Chemistry. 32(7), e4399.
• [24] Kaloğlu, M., Kaloğlu, N., Özdemir, İ. 2018. ChemistrySelect. 3, 5600-5607.
• [25] Kaloğlu, N., Achard, M., Bruneau, C., Özdemir, İ. European Journal of Inorganic Chemistry. 2019. 21, 2598–2606.
• [26] Sundararaju, B., Tang, Z., Achard, M., Sharma, G.V.M., Toupet, L., Bruneau,C. 2010. Advanced Synthesis & Catalysis. 352 (18) 3141–3146.