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Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu ve Aminlerin Alkilasyonundaki Uygulamaları

Year 2018, Volume: 22 Issue: Special, 127 - 132, 05.10.2018

Öznur Doğan Ulu

Abstract

Bu çalışmada, benzhidril grubu içeren benzimidazolyum tuzları ilk olarak Ag2O ile etkileştirilerek Ag-NHC kompleksi elde edildi. Elde edilen Ag-NHC kompleksi izole edilmeden [RuCl2(p-simen)2]2 ile etkileştirilerek iki yeni rutenyum N-heterosiklik karben (Ru-NHC) kompleksi sentezlendi. Sentezlenen komplekslerin yapıları 1H-NMR, 13C-NMR, FT-IR ve elementel analiz yöntemleriyle karakterize edildi. Ayrıca, sentezlenen Ru-NHC kompleksleri, aminlerin alkoller ile alkilasyonu tepkimelerinde katalizör olarak kullanıldı. Alkilasyon tepkimesi, çevreye duyarlı ve ekonomik açıdan avantajlı olduğu için ödünç hidrojen metodolojisi yöntemi ile yapıldı. Bütün tepkimelerde %1 mol katalizör miktarı kullanıldı.  Elde edilen sonuçlar katalizörlerin N-alkilasyon tepkimesinde aktif olduğunu gösterdi. Ayrıca bu çalışmada kullanılan katalizörler literatürdeki benzerleriyle kıyaslandığında aktivitelerinin yaklaşık olarak aynı olduğu görülmüştür.

Keywords

Rutenyum katalizörü N-Alkilasyon; Amin; N-heterosiklik karben

References

  • [1] Lawrence, S.A. 2004. Amines: Synthesis, Properties and Applications, Cambridge University, Cambridge.
  • [2] Shi, S.-L, Buchwald, S.L. 2015. Copper-Catalysed Selective Hydroamination Reactions of Alkynes. Nature Chemistry, 7 (2015), 38-44.
  • [3] Kolesnikov, P.N., Yagafarov, N.Z., Usanov, D.L., Chusov, D.2015. Ruthenium-Catalyzed Reductive Amination without an External Hydrogen Source. Organic Letters, 17 (2015), 173-175.
  • [4] Salomé, C., Schmitt, M., Bourguignon, J.-J. 2012. Novel Access to 1,4-benzodiazepin-2-ones via the Buchwald Reaction and Application to the Synthesis of Novel Heterocyclics. Tetrahedron Letters, 53 (2012), 1033-1035.
  • [5] Ma, X., Su, C., Xu, Q. 2016. N-Alkylation by Hydrogen Autotransfer Reactions. 291-365. Guillena ,G., Ramón, D.J., ed. 2016. Hydrogen Transfer Reactions,Topics in Current Chemistry. Springer International Publishing, Switzerland,387 s.
  • [6] Grigg, R., Mitchell, T.R., Sutthivaiyakit, B.S., Tongpenyai, N. J.1981. Transition Metal-Catalysed N-alkylation of Amines by Alcohols. Journal of the Chemical Society, Chemical Communications, (1981),611-612.
  • [7] Watanabe, T. Y., Oshugi, Y. 1981. The Ruthenium Catalyzed N-Alkylation and N-Heterocyclization of Aniline Using Alcohols and Aldehydes. Tetrahedron Letters, 22 (1981),2667-2770.
  • [8] Bähn, S., Imm, S., Mevius, K., Neubert, L., Williams, J.M.J., Beller, M. 2010. Selective Ruthenium-Catalyzed N-Alkylation of Indoles by Using Alcohols. Chemistry A. European Journal, 16 (2010), 3590-3593.
  • [9] Ma, W.M.J., James, T.D., Williams, J.M.J. 2013. Synthesis of Amines with Pendant Boronic Esters by Borrowing Hydrogen Catalysis Organic Letters, 15 (2013), 4850-4853.
  • [10] Zou, Q., Wang, C., Smith, J., Xue, D., Xiao, J. 2015. Alkylation of Amines with Alcohols and Amines by a Single Catalyst under Mild Conditions. Chemistry A. European Journal, 21 (2015), 9656-9661.
  • [11] Chang, Y.-H., Tanigawa, I., Takeuchi, K., Ozawa, F. 2016. Iridium(I) Complexes Bearing a Noninnocent PNP-Pincer-Type Phosphaalkene -Ligand: Catalytic Application in the Base-Free N-Alkylation of Amines with Alcohols. European. Journal of Inorganic Chemistry, (2016), 754-760.
  • [12] Yan, T., Feringa, B.L.T., Barta, K. 2014. Iron Catalysed Direct Alkylation Of Amines With Alcohols. Natural Communications, 5 (2014), 5602-5608.
  • [13] Öfele, K. 1968. 1,3-Dimethyl-4-imidazolinyliden-(2)-Pentacarbonylchrom Ein Neuer Übergangsmetall Carben-Komplex. Journal of Organometallic Chemistry, 12 (1968), 42–43.
  • [14] Wanzlik, H.-W., Schönherr, H.-J., 1968. Direct Synthesis of a Mercury Salt-Carbene Complex. Angewandte Chemie, 7 (1968), 141-142.
  • [15] Arduengo, A.J., Harlow, L.R., Kline, M. 1991. A Stable Crystalline Carbene. Journal Of American Chemical Society, 113, (1991) 361-363.
  • [16] Díez-González, S., Marion, N., Nolan, S.P. 2009. N-Heterocyclic Carbenes in Late Transition Metal Catalysis. Chemical. Reviews. 109, (2009) 3612–3676.
  • [17] Díez-González S. (Ed.), 2011. N-Heterocyclic Carbenes. From Laboratory Curiosities to Efficient Synthetic Tools, Royal Society of Chemistry, Cambridge,U.K,.
  • [18] Cazin C.S.J. (Ed.). 2011. N-Heterocyclic Carbenes İn Transition Metal Catalysis And Organocatalysis, in: Catalysis by Metal Complexes, Vol. 32, Springer Dordrecht, The Netherlands.
  • [19] Li, W., Wiesenfeldt,M.P., Glorius F. 2017. Ruthenium–NHC–Diamine Catalyzed Enantioselective Hydrogenation of Isocoumarins. Journal Of American Chemical Society, 7 (2017), 2585–2588.
  • [20] Song, C., Ma, C., Ma, Y., Feng, W., Ma, S., Chai, Q., Andrus, M.B. 2005. Bis-Paracyclophane N-Heterocyclic Carbene–Ruthenium Catalyzed Asymmetric Ketone Hydrosilylation. Tetrahedron Letters, 46 (2005), 3241-3244.
  • [21] Engl, P.S., Santiago, C.B., Gordon , C.P., Liao, W-C., Fedorov, A., Copéret, C., Sigman, M.S.,Togni, A. 2017. Exploiting and Understanding the Selectivity of Ru-N-Heterocyclic Carbene Metathesis Catalysts for the Ethenolysis of Cyclic Olefins to α,ω-Dienes. Journal Of American Chemical Society, , 37(2017) 13117–13125.
  • [22] Yasar, S., Dogan, O., Ozdemir,I., Çetinkaya, B. 2008. Ruthenium N-Heterocyclic–Carbene Catalyzed Diarylation of Arene C H Bond. Applied of Organometallic Chemistry, 22, (2008),314-318.
  • [23] Gnanamgari, D., Sauer, E.L.O., Schley, N.D., Butler, C., Incarvito, C.D., Crabtree, R.H. 2009. Iridium and Ruthenium Complexes with Chelating N-Heterocyclic Carbenes: Efficient Catalysts for Transfer Hydrogenation, β-Alkylation of Alcohols, and N-Alkylation of Amines. Organometallics, 28 (2009), 321-325.
  • [24] Wang, D., Guo, X-G., Wang, C-X., Wang, Y-N., Zhong, R., Zhu, X-H Cai, L-H., Gao, Z-W., Hou, X-F. 2013. An Efficient and Recyclable Catalyst for N-Alkylation of Amines and β-Alkylation of Secondary Alcohols with Primary Alcohols: SBA-15 Supported N-Heterocyclic Carbene Iridium Complex. Advanced Synthesis Catalysis, 355 (2013),1117-1125.
  • [25] Li, J-Q., Andersson, P.G. 2013. Room Temperature And Solvent-Free İridium-Catalyzed Selective Alkylation Of Anilines With Alcohols. Chemical. Communications, 49 (2013), 6131-6133.
  • [26] Costa, A.P., Viciano, M., Sanaú, M., Merino, S., 4 Tejeda, J., Peris, E., Royo, B. 2008. First Cp*-Functionalized N-Heterocyclic Carbene and Its Coordination to Iridium. Study of the Catalytic Properties. Organometallics, 27 ( 2008), 1305-1309.
  • [27] Chang, Y-H., Fu, C-F., Liu, Y-H., Peng, S-M., Chen, J.T., Liu. S-T. 2009. Synthesis, Characterization And Catalytic Activity Of Saturated And Unsaturated N-Heterocyclic Carbene Iridium(I) Complexes. Dalton Transactions, (2009), 861-867.
  • [28] Kuo, H-Y., Liu, Y-H., Peng, S-M., Liu, S-T. 2012. N,N′-Dialkylation Catalyzed by Bimetallic Iridium Complexes Containing a Saturated Bis-N-Heterocyclic Carbene (NHC) Ligand. Organometallics, 31 (2012), 7248-7255.
  • [29] Bartoszewicz, A., Marcos, R., Sahoo, S., Inge, A.K., Zou, X., Martín-Matute, B. 2012. A Highly Active Bifunctional Iridium Complex with an Alcohol/Alkoxide-Tethered N-Heterocyclic Carbene for Alkylation of Amines with Alcohols. Chemistry A. European Journal, 18 (2012), 14510-14519.
  • [30] Yu X-J, He H-Y, Yang L, Fu, H-Y., Zheng, X-L., Chen, H., Li, R-X. 2017. Hemilabile N-Heterocyclic Carbene (NHC)-Nitrogen-Phosphine Mediated Ru (II)-Catalyzed N-Alkylation of Aromatic Amine with Alcohol Efficiently. Catalysis Communications, 95 (2017),54-57.
  • [31] Kaloglu, N., Ozdemir, I., Gürbüz, N., Achard, M., Bruneau, C. 2016. Benzimidazolium Sulfonate Ligand Precursors And Application In Ruthenium-Catalyzed Aromatic Amine Alkylation With Alcohols. Catalysis Communications, 74 ( 2016), 33-38.
  • [32] Şahin, Z., Gürbüz, N., Ozdemir, I., Şahin, O., Büyükgüngör, O., Achard, M., Bruneau, C. 2015. N-Alkylation and N,C-Dialkylation of Amines with Alcohols in the Presence of Ruthenium Catalysts with Chelating N-Heterocyclic Carbene Ligands. Organometallics, 34 ( 2015), 2296-2304.
  • [33] Ozdemir, I., Demir Düsünceli, S., Kaloglu, N., Achard, M., Bruneau, C. 2015. Synthesis of Ruthenium N-Heterocyclic Carbene Complexes and Their Catalytic Activity for Β-Alkylation of Tertiary Cyclic Amines. Jornal of Organometallic Chemistry, 799-800 (2015), 311-315.
  • [34] Dogan Ulu, O., Gürbüz, N., Ozdemir, I. 2018. Alkylation of Cyclic Amines with Alcohols Catalyzed by Ru(II)Complexes Bearing N-Heterocyclic Carbenes. Tetrahedron, 74 (2018), 645-651.

Year 2018, Volume: 22 Issue: Special, 127 - 132, 05.10.2018

Öznur Doğan Ulu

Abstract

References

  • [1] Lawrence, S.A. 2004. Amines: Synthesis, Properties and Applications, Cambridge University, Cambridge.
  • [2] Shi, S.-L, Buchwald, S.L. 2015. Copper-Catalysed Selective Hydroamination Reactions of Alkynes. Nature Chemistry, 7 (2015), 38-44.
  • [3] Kolesnikov, P.N., Yagafarov, N.Z., Usanov, D.L., Chusov, D.2015. Ruthenium-Catalyzed Reductive Amination without an External Hydrogen Source. Organic Letters, 17 (2015), 173-175.
  • [4] Salomé, C., Schmitt, M., Bourguignon, J.-J. 2012. Novel Access to 1,4-benzodiazepin-2-ones via the Buchwald Reaction and Application to the Synthesis of Novel Heterocyclics. Tetrahedron Letters, 53 (2012), 1033-1035.
  • [5] Ma, X., Su, C., Xu, Q. 2016. N-Alkylation by Hydrogen Autotransfer Reactions. 291-365. Guillena ,G., Ramón, D.J., ed. 2016. Hydrogen Transfer Reactions,Topics in Current Chemistry. Springer International Publishing, Switzerland,387 s.
  • [6] Grigg, R., Mitchell, T.R., Sutthivaiyakit, B.S., Tongpenyai, N. J.1981. Transition Metal-Catalysed N-alkylation of Amines by Alcohols. Journal of the Chemical Society, Chemical Communications, (1981),611-612.
  • [7] Watanabe, T. Y., Oshugi, Y. 1981. The Ruthenium Catalyzed N-Alkylation and N-Heterocyclization of Aniline Using Alcohols and Aldehydes. Tetrahedron Letters, 22 (1981),2667-2770.
  • [8] Bähn, S., Imm, S., Mevius, K., Neubert, L., Williams, J.M.J., Beller, M. 2010. Selective Ruthenium-Catalyzed N-Alkylation of Indoles by Using Alcohols. Chemistry A. European Journal, 16 (2010), 3590-3593.
  • [9] Ma, W.M.J., James, T.D., Williams, J.M.J. 2013. Synthesis of Amines with Pendant Boronic Esters by Borrowing Hydrogen Catalysis Organic Letters, 15 (2013), 4850-4853.
  • [10] Zou, Q., Wang, C., Smith, J., Xue, D., Xiao, J. 2015. Alkylation of Amines with Alcohols and Amines by a Single Catalyst under Mild Conditions. Chemistry A. European Journal, 21 (2015), 9656-9661.
  • [11] Chang, Y.-H., Tanigawa, I., Takeuchi, K., Ozawa, F. 2016. Iridium(I) Complexes Bearing a Noninnocent PNP-Pincer-Type Phosphaalkene -Ligand: Catalytic Application in the Base-Free N-Alkylation of Amines with Alcohols. European. Journal of Inorganic Chemistry, (2016), 754-760.
  • [12] Yan, T., Feringa, B.L.T., Barta, K. 2014. Iron Catalysed Direct Alkylation Of Amines With Alcohols. Natural Communications, 5 (2014), 5602-5608.
  • [13] Öfele, K. 1968. 1,3-Dimethyl-4-imidazolinyliden-(2)-Pentacarbonylchrom Ein Neuer Übergangsmetall Carben-Komplex. Journal of Organometallic Chemistry, 12 (1968), 42–43.
  • [14] Wanzlik, H.-W., Schönherr, H.-J., 1968. Direct Synthesis of a Mercury Salt-Carbene Complex. Angewandte Chemie, 7 (1968), 141-142.
  • [15] Arduengo, A.J., Harlow, L.R., Kline, M. 1991. A Stable Crystalline Carbene. Journal Of American Chemical Society, 113, (1991) 361-363.
  • [16] Díez-González, S., Marion, N., Nolan, S.P. 2009. N-Heterocyclic Carbenes in Late Transition Metal Catalysis. Chemical. Reviews. 109, (2009) 3612–3676.
  • [17] Díez-González S. (Ed.), 2011. N-Heterocyclic Carbenes. From Laboratory Curiosities to Efficient Synthetic Tools, Royal Society of Chemistry, Cambridge,U.K,.
  • [18] Cazin C.S.J. (Ed.). 2011. N-Heterocyclic Carbenes İn Transition Metal Catalysis And Organocatalysis, in: Catalysis by Metal Complexes, Vol. 32, Springer Dordrecht, The Netherlands.
  • [19] Li, W., Wiesenfeldt,M.P., Glorius F. 2017. Ruthenium–NHC–Diamine Catalyzed Enantioselective Hydrogenation of Isocoumarins. Journal Of American Chemical Society, 7 (2017), 2585–2588.
  • [20] Song, C., Ma, C., Ma, Y., Feng, W., Ma, S., Chai, Q., Andrus, M.B. 2005. Bis-Paracyclophane N-Heterocyclic Carbene–Ruthenium Catalyzed Asymmetric Ketone Hydrosilylation. Tetrahedron Letters, 46 (2005), 3241-3244.
  • [21] Engl, P.S., Santiago, C.B., Gordon , C.P., Liao, W-C., Fedorov, A., Copéret, C., Sigman, M.S.,Togni, A. 2017. Exploiting and Understanding the Selectivity of Ru-N-Heterocyclic Carbene Metathesis Catalysts for the Ethenolysis of Cyclic Olefins to α,ω-Dienes. Journal Of American Chemical Society, , 37(2017) 13117–13125.
  • [22] Yasar, S., Dogan, O., Ozdemir,I., Çetinkaya, B. 2008. Ruthenium N-Heterocyclic–Carbene Catalyzed Diarylation of Arene C H Bond. Applied of Organometallic Chemistry, 22, (2008),314-318.
  • [23] Gnanamgari, D., Sauer, E.L.O., Schley, N.D., Butler, C., Incarvito, C.D., Crabtree, R.H. 2009. Iridium and Ruthenium Complexes with Chelating N-Heterocyclic Carbenes: Efficient Catalysts for Transfer Hydrogenation, β-Alkylation of Alcohols, and N-Alkylation of Amines. Organometallics, 28 (2009), 321-325.
  • [24] Wang, D., Guo, X-G., Wang, C-X., Wang, Y-N., Zhong, R., Zhu, X-H Cai, L-H., Gao, Z-W., Hou, X-F. 2013. An Efficient and Recyclable Catalyst for N-Alkylation of Amines and β-Alkylation of Secondary Alcohols with Primary Alcohols: SBA-15 Supported N-Heterocyclic Carbene Iridium Complex. Advanced Synthesis Catalysis, 355 (2013),1117-1125.
  • [25] Li, J-Q., Andersson, P.G. 2013. Room Temperature And Solvent-Free İridium-Catalyzed Selective Alkylation Of Anilines With Alcohols. Chemical. Communications, 49 (2013), 6131-6133.
  • [26] Costa, A.P., Viciano, M., Sanaú, M., Merino, S., 4 Tejeda, J., Peris, E., Royo, B. 2008. First Cp*-Functionalized N-Heterocyclic Carbene and Its Coordination to Iridium. Study of the Catalytic Properties. Organometallics, 27 ( 2008), 1305-1309.
  • [27] Chang, Y-H., Fu, C-F., Liu, Y-H., Peng, S-M., Chen, J.T., Liu. S-T. 2009. Synthesis, Characterization And Catalytic Activity Of Saturated And Unsaturated N-Heterocyclic Carbene Iridium(I) Complexes. Dalton Transactions, (2009), 861-867.
  • [28] Kuo, H-Y., Liu, Y-H., Peng, S-M., Liu, S-T. 2012. N,N′-Dialkylation Catalyzed by Bimetallic Iridium Complexes Containing a Saturated Bis-N-Heterocyclic Carbene (NHC) Ligand. Organometallics, 31 (2012), 7248-7255.
  • [29] Bartoszewicz, A., Marcos, R., Sahoo, S., Inge, A.K., Zou, X., Martín-Matute, B. 2012. A Highly Active Bifunctional Iridium Complex with an Alcohol/Alkoxide-Tethered N-Heterocyclic Carbene for Alkylation of Amines with Alcohols. Chemistry A. European Journal, 18 (2012), 14510-14519.
  • [30] Yu X-J, He H-Y, Yang L, Fu, H-Y., Zheng, X-L., Chen, H., Li, R-X. 2017. Hemilabile N-Heterocyclic Carbene (NHC)-Nitrogen-Phosphine Mediated Ru (II)-Catalyzed N-Alkylation of Aromatic Amine with Alcohol Efficiently. Catalysis Communications, 95 (2017),54-57.
  • [31] Kaloglu, N., Ozdemir, I., Gürbüz, N., Achard, M., Bruneau, C. 2016. Benzimidazolium Sulfonate Ligand Precursors And Application In Ruthenium-Catalyzed Aromatic Amine Alkylation With Alcohols. Catalysis Communications, 74 ( 2016), 33-38.
  • [32] Şahin, Z., Gürbüz, N., Ozdemir, I., Şahin, O., Büyükgüngör, O., Achard, M., Bruneau, C. 2015. N-Alkylation and N,C-Dialkylation of Amines with Alcohols in the Presence of Ruthenium Catalysts with Chelating N-Heterocyclic Carbene Ligands. Organometallics, 34 ( 2015), 2296-2304.
  • [33] Ozdemir, I., Demir Düsünceli, S., Kaloglu, N., Achard, M., Bruneau, C. 2015. Synthesis of Ruthenium N-Heterocyclic Carbene Complexes and Their Catalytic Activity for Β-Alkylation of Tertiary Cyclic Amines. Jornal of Organometallic Chemistry, 799-800 (2015), 311-315.
  • [34] Dogan Ulu, O., Gürbüz, N., Ozdemir, I. 2018. Alkylation of Cyclic Amines with Alcohols Catalyzed by Ru(II)Complexes Bearing N-Heterocyclic Carbenes. Tetrahedron, 74 (2018), 645-651.
There are 34 citations in total.

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Journal Section Articles
Authors

Öznur Doğan Ulu

Publication Date October 5, 2018
Published in Issue Year 2018 Volume: 22 Issue: Special

Cite

APA Doğan Ulu, Ö. (2018). Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu ve Aminlerin Alkilasyonundaki Uygulamaları. Süleyman Demirel Üniversitesi Fen Bilimleri Enstitüsü Dergisi, 22, 127-132.
AMA Doğan Ulu Ö. Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu ve Aminlerin Alkilasyonundaki Uygulamaları. SDÜ Fen Bil Enst Der. October 2018;22:127-132.
Chicago Doğan Ulu, Öznur. “Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu Ve Aminlerin Alkilasyonundaki Uygulamaları”. Süleyman Demirel Üniversitesi Fen Bilimleri Enstitüsü Dergisi 22, October (October 2018): 127-32.
EndNote Doğan Ulu Ö (October 1, 2018) Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu ve Aminlerin Alkilasyonundaki Uygulamaları. Süleyman Demirel Üniversitesi Fen Bilimleri Enstitüsü Dergisi 22 127–132.
IEEE Ö. Doğan Ulu, “Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu ve Aminlerin Alkilasyonundaki Uygulamaları”, SDÜ Fen Bil Enst Der, vol. 22, pp. 127–132, 2018.
ISNAD Doğan Ulu, Öznur. “Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu Ve Aminlerin Alkilasyonundaki Uygulamaları”. Süleyman Demirel Üniversitesi Fen Bilimleri Enstitüsü Dergisi 22 (October 2018), 127-132.
JAMA Doğan Ulu Ö. Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu ve Aminlerin Alkilasyonundaki Uygulamaları. SDÜ Fen Bil Enst Der. 2018;22:127–132.
MLA Doğan Ulu, Öznur. “Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu Ve Aminlerin Alkilasyonundaki Uygulamaları”. Süleyman Demirel Üniversitesi Fen Bilimleri Enstitüsü Dergisi, vol. 22, 2018, pp. 127-32.
Vancouver Doğan Ulu Ö. Yeni Ru-NHC Komplekslerinin Sentezi, Karakterizasyonu ve Aminlerin Alkilasyonundaki Uygulamaları. SDÜ Fen Bil Enst Der. 2018;22:127-32.
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