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Asimetrik Michael Katılma Tepkimesi için Prolin bazlı β-Hidroksiamit Organokatalizörü

Year 2022, Volume: 5 Issue: 1, 13 - 17, 15.06.2022
https://doi.org/10.53448/akuumubd.1111800

Abstract

Michael katılması gibi C-C bağı oluşturma yeteneğine sahip reaksiyon tiplerinde, kiral organokatalizör uygulamaları son yılların önemli araştırma alanlarındandır. Organik reaksiyon tiplerinden önemli çalışmalarından biri olan Michael katılmasına en iyi örneklerden biri de organokatalizörler varlığında nitroolefinlerin ketonlar ile reaksiyonudur. Bu çalışmada; L-prolin bazlı amit türevi, ılımlı bir verim ile sentezi gerçekleştirilmiş ve yapısı çeşitli teknikler ile aydınlatılmıştır. Sentezi gerçekleştirilen bu bileşiğin; organokatalizör olarak, Michael katılma çalışmalarında enantiyomerik aşırılık (e.e.) üzerine etkisi incelenmiş ve en iyi enantiyomerik aşırılık değerinin karbontetra klorür (CCl4) içinde ve %65 olduğu tespit edilmiştir.

References

  • Bulger, P.G., 2012. Industrial Applications of Organocatalysis, Editor(s): Erick M. Carreira, Hisashi Yamamoto, Comprehensive Chirality, Elsevier, 228-252.
  • Barrulas, P.C., Genoni, A., Benaglia, M., Burke A.J., 2014. Cinchona-Derived Picolinamides: Effective Organocatalysts for Stereoselective Imine Hydrosilylation. Eur. J. Org. Chem. 7339–7342.
  • Carlone, A. and Bernardi, L. 2019. Enantioselective organocatalytic approaches to active pharmaceutical ingredients – selected industrial examples Physical Sciences Reviews, 4, 20180097.
  • Susam, Z.D., Tanyeli, C., 2021, Recyclable Organocatalysts in Asymmetric Synthesis. Asian Journal of Organic Chemistry, 10, 1251-1266.
  • Dalko, P.I., Moisan, L. 2004, In the golden age of organocatalysis. Angewandte Chemie International Edition., 43, 5138–5175.
  • List, B., 2006. The ying and yang of asymmetric aminocatalysis. Chemical Communications. 819–824. https://www.nobelprize.org/prizes/chemistry/2021/press-release/ (20.04.2022)
  • List, B., 2004. Organocatalysis: a complementary catalysis strategy advances organic synthesis. Advanced Synthesis & Catalysis, 346, 1021.
  • Bozkurt, S., Durmaz, M., Yilmaz, M., Sirit, A., 2008. Calixarene-based chiral phase-transfer catalysts derived from cinchona alkaloids for enantioselective synthesis of α-amino acids. Tetrahedron: Asymmetry 19, 618-623.
  • Liu, L., Liu, ZT., Liu, ZW. et al. 2010. L-Proline catalyzed aldol reactions between acetone and aldehydes in supercritical fluids: An environmentally friendly reaction procedure. Sci. China Chem. 53, 1586–1591.
  • Jin, H., Kim, S.T., Hwang, G.S., Ryu, D.H., 2016. L-Proline Derived Bifunctional Organocatalysts: Enantioselective Michael Addition of Dithiomalonates to trans-β-Nitroolefins. The Journal of Organic Chemistry 81, 3263-3274.
  • Kumar, GR., Ramesh, B., Yarlagadda, S., Sridhar, B., Reddy, B.V.S, 2019. Organocatalytic Enantioselective Mannich Reaction: Direct Access to Chiral β-Amino Esters. ACS Omega 4, 2168-2177.
  • Castan, A. Badorrey, R., Galvez J.A., Lopez-Ram-de-Viu, P., DiazVillegasde, M.D., 2018. Michael addition of carbonyl compounds to nitroolefins under the catalysis of new pyrrolidine-based bifunctional organocatalysts. Organic & Biomolecular Chemistry 16, 924-935
  • Durmaz, M., Sirit, A. 2013. Application of L-prolinamides as highly efficient organocatalysts for the asymmetric Michael addition of unmodified aldehydes to nitroalkenes. Supramol. Chem. 25, 292–301.
  • Naziroglu, H.N., Durmaz, M., Bozkurt, S., Demir, A.S., Sirit, A. 2012. Application of L-prolinamides as highly efficient organocatalysts for the asymmetric Michael addition of unmodified aldehydes to nitroalkenes. Tetrahedron: Asymmetry 23, 164-169.
  • Vural, U., Durmaz, M., Sirit, A. 2016. A novel calix [4] arene-based bifunctional squaramide organocatalyst for enantioselective Michael addition of acetylacetone to nitroolefins. Organic Chemistry Frontiers 3, 730-736.
  • Shim, J.H., Lee, M.J., Lee, M.H., Kim, B.,S., Ha, D.C., 2020. Enantioselective organocatalytic Michael reactions using chiral (R,R)-1,2-diphenylethylenediamine derived thioureas. RSV Adv. 10, 31808.
  • Zhu, S., Yu, S., Wang, Y. and Ma, D. 2010. Organocatalytic Michael Addition of Aldehydes to Protected 2-Amino-1-Nitroethenes: The Practical Syntheses of Oseltamivir (Tamiflu) and Substituted 3-Aminopyrrolidines. Angew. Chem. Int. Ed., 49, 4656-4660.
  • Xu, K., Zhang, S., Hu, Y., Zha, Z. and Wang, Z. 2013. Asymmetric Michael Reaction Catalyzed by Proline Lithium Salt: Efficient Synthesis of L-Proline and Isoindoloisoquinolinone Derivatives. Chem. Eur. J., 19, 3573-3578.
  • Yan, Z.Y., Niu, Y.N., Wei, H.L., Wu, L.Y., Zhao, Y.B., Liang, M. 2006. Combining proline and ‘click chemistry’: a class of versatile organocatalysts for the highly diastereo- and enantioselective Michael addition in water. Tetrahedron: Asymmetry 17, 3288-3293.
  • Yumiko, S., 2018. Asymmetric Michael Addition Mediated by Chiral Ionic Liquids. Mini-Reviews in Organic Chemistry 15, 236-245.
  • Michael, H., Haindl, M.H., Hioe, J., Gschwind, R.M., 2015. The Proline Enamine Formation Pathway Revisited in Dimethyl Sulfoxide: Rate Constants Determined via NMR. Journal of the American Chemical Society 137, 12835-12842.
  • Hong, H., Wang, H., Zheng, C., Zhao, G., Shang, Y., 2021. Organophosphine bearing multiple hydrogen-bond donors for asymmetric Michael addition reaction of 1-oxoindane-2-carboxylic acid ester via dual-reagent catalysis. Chinese Chemical Letters, 32, 708-712.
  • Bozkurt, S., Yilmaz, M., Sirit, A., 2012. Chiral Calix[4]arenes Bearing Amino Alcohol Functionality as Membrane Carriers for Transport of Chiral Amino Acid Methylesters and Mandelic Acid. Chirality, 24, 129-136

Prolines Based β-Hydroxyamide as Organocatalysts for Use in Asymmetric Michael Addition

Year 2022, Volume: 5 Issue: 1, 13 - 17, 15.06.2022
https://doi.org/10.53448/akuumubd.1111800

Abstract

Applications of chiral organocatalysts in reaction types capable of forming C-C bonds, such as Michael addition, are one of the important research areas of recent years. One of the best examples of Michael addition, one of the important works of organic reaction types, is the reaction of nitroolefins with ketones in the presence of organocatalysts. In this study, L-proline-based amide derivative was synthesized with moderate yield and its structure was elucidated by various techniques. As an organocatalyst, its effect on enantiomeric excess (e.e.) was investigated in Michael addition studies and the best enantiomeric excess value was found to be 65% in carbontetra chloride (CCl4).

Thanks

The author would like to thank Prof. Dr. Abdulkadir Sırıt for support during the preparation this study.

References

  • Bulger, P.G., 2012. Industrial Applications of Organocatalysis, Editor(s): Erick M. Carreira, Hisashi Yamamoto, Comprehensive Chirality, Elsevier, 228-252.
  • Barrulas, P.C., Genoni, A., Benaglia, M., Burke A.J., 2014. Cinchona-Derived Picolinamides: Effective Organocatalysts for Stereoselective Imine Hydrosilylation. Eur. J. Org. Chem. 7339–7342.
  • Carlone, A. and Bernardi, L. 2019. Enantioselective organocatalytic approaches to active pharmaceutical ingredients – selected industrial examples Physical Sciences Reviews, 4, 20180097.
  • Susam, Z.D., Tanyeli, C., 2021, Recyclable Organocatalysts in Asymmetric Synthesis. Asian Journal of Organic Chemistry, 10, 1251-1266.
  • Dalko, P.I., Moisan, L. 2004, In the golden age of organocatalysis. Angewandte Chemie International Edition., 43, 5138–5175.
  • List, B., 2006. The ying and yang of asymmetric aminocatalysis. Chemical Communications. 819–824. https://www.nobelprize.org/prizes/chemistry/2021/press-release/ (20.04.2022)
  • List, B., 2004. Organocatalysis: a complementary catalysis strategy advances organic synthesis. Advanced Synthesis & Catalysis, 346, 1021.
  • Bozkurt, S., Durmaz, M., Yilmaz, M., Sirit, A., 2008. Calixarene-based chiral phase-transfer catalysts derived from cinchona alkaloids for enantioselective synthesis of α-amino acids. Tetrahedron: Asymmetry 19, 618-623.
  • Liu, L., Liu, ZT., Liu, ZW. et al. 2010. L-Proline catalyzed aldol reactions between acetone and aldehydes in supercritical fluids: An environmentally friendly reaction procedure. Sci. China Chem. 53, 1586–1591.
  • Jin, H., Kim, S.T., Hwang, G.S., Ryu, D.H., 2016. L-Proline Derived Bifunctional Organocatalysts: Enantioselective Michael Addition of Dithiomalonates to trans-β-Nitroolefins. The Journal of Organic Chemistry 81, 3263-3274.
  • Kumar, GR., Ramesh, B., Yarlagadda, S., Sridhar, B., Reddy, B.V.S, 2019. Organocatalytic Enantioselective Mannich Reaction: Direct Access to Chiral β-Amino Esters. ACS Omega 4, 2168-2177.
  • Castan, A. Badorrey, R., Galvez J.A., Lopez-Ram-de-Viu, P., DiazVillegasde, M.D., 2018. Michael addition of carbonyl compounds to nitroolefins under the catalysis of new pyrrolidine-based bifunctional organocatalysts. Organic & Biomolecular Chemistry 16, 924-935
  • Durmaz, M., Sirit, A. 2013. Application of L-prolinamides as highly efficient organocatalysts for the asymmetric Michael addition of unmodified aldehydes to nitroalkenes. Supramol. Chem. 25, 292–301.
  • Naziroglu, H.N., Durmaz, M., Bozkurt, S., Demir, A.S., Sirit, A. 2012. Application of L-prolinamides as highly efficient organocatalysts for the asymmetric Michael addition of unmodified aldehydes to nitroalkenes. Tetrahedron: Asymmetry 23, 164-169.
  • Vural, U., Durmaz, M., Sirit, A. 2016. A novel calix [4] arene-based bifunctional squaramide organocatalyst for enantioselective Michael addition of acetylacetone to nitroolefins. Organic Chemistry Frontiers 3, 730-736.
  • Shim, J.H., Lee, M.J., Lee, M.H., Kim, B.,S., Ha, D.C., 2020. Enantioselective organocatalytic Michael reactions using chiral (R,R)-1,2-diphenylethylenediamine derived thioureas. RSV Adv. 10, 31808.
  • Zhu, S., Yu, S., Wang, Y. and Ma, D. 2010. Organocatalytic Michael Addition of Aldehydes to Protected 2-Amino-1-Nitroethenes: The Practical Syntheses of Oseltamivir (Tamiflu) and Substituted 3-Aminopyrrolidines. Angew. Chem. Int. Ed., 49, 4656-4660.
  • Xu, K., Zhang, S., Hu, Y., Zha, Z. and Wang, Z. 2013. Asymmetric Michael Reaction Catalyzed by Proline Lithium Salt: Efficient Synthesis of L-Proline and Isoindoloisoquinolinone Derivatives. Chem. Eur. J., 19, 3573-3578.
  • Yan, Z.Y., Niu, Y.N., Wei, H.L., Wu, L.Y., Zhao, Y.B., Liang, M. 2006. Combining proline and ‘click chemistry’: a class of versatile organocatalysts for the highly diastereo- and enantioselective Michael addition in water. Tetrahedron: Asymmetry 17, 3288-3293.
  • Yumiko, S., 2018. Asymmetric Michael Addition Mediated by Chiral Ionic Liquids. Mini-Reviews in Organic Chemistry 15, 236-245.
  • Michael, H., Haindl, M.H., Hioe, J., Gschwind, R.M., 2015. The Proline Enamine Formation Pathway Revisited in Dimethyl Sulfoxide: Rate Constants Determined via NMR. Journal of the American Chemical Society 137, 12835-12842.
  • Hong, H., Wang, H., Zheng, C., Zhao, G., Shang, Y., 2021. Organophosphine bearing multiple hydrogen-bond donors for asymmetric Michael addition reaction of 1-oxoindane-2-carboxylic acid ester via dual-reagent catalysis. Chinese Chemical Letters, 32, 708-712.
  • Bozkurt, S., Yilmaz, M., Sirit, A., 2012. Chiral Calix[4]arenes Bearing Amino Alcohol Functionality as Membrane Carriers for Transport of Chiral Amino Acid Methylesters and Mandelic Acid. Chirality, 24, 129-136
There are 23 citations in total.

Details

Primary Language English
Subjects Engineering
Journal Section Articles
Authors

Selahattin Bozkurt 0000-0002-9147-5938

Publication Date June 15, 2022
Submission Date April 30, 2022
Published in Issue Year 2022 Volume: 5 Issue: 1

Cite

APA Bozkurt, S. (2022). Prolines Based β-Hydroxyamide as Organocatalysts for Use in Asymmetric Michael Addition. Afyon Kocatepe Üniversitesi Uluslararası Mühendislik Teknolojileri Ve Uygulamalı Bilimler Dergisi, 5(1), 13-17. https://doi.org/10.53448/akuumubd.1111800