DOI: https://doi.org/10.9767/bcrec.16.4.11487.796-803

DFT Study on the Reaction Mechanism of Cyclization of 2-Hydroxy Chalcone Catalyzed by Bronsted Acid with M06-2X Functional

1Physical Chemistry Group, Department of Chemistry, Institut Teknologi Bandung, Bandung 40116, Indonesia

2Organic Chemistry Group, Department of Chemistry, Institut Teknologi Bandung, Bandung 40116, Indonesia

Received: 20 Jun 2021; Revised: 21 Aug 2021; Accepted: 22 Aug 2021; Available online: 31 Aug 2021; Published: 20 Dec 2021.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2021 by Authors, Published by BCREC Group
Creative Commons License This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.

Citation Format:
Cover Image
Abstract

Flavanones are one of the flavonoid group that has wide variety of applications such as a precursors in drug discovery. In the laboratory, flavanone is often synthesized from chalcone compounds. The conversion of chalcone to flavanone can be catalyzed by bronsted acid. The reaction mechanism for this process is proposed through the Michael addition reaction, however, the energetic details and the rate determining step for this reaction is not certainly known. This research aimed to investigate the reaction mechanism for chalcone-flavanone conversion with the present of bronsted acid as catalyst and also studied the effect of the solvent on the reaction energy profile with computational method. In this study, the modeling of the reaction mechanism for the said reaction was carried out using the DFT computational method with M06-2X functional. The computation was done both in the gas phase and in present of the solvent effect using the PCM models. The results showed that the mechanism of chalcone-flavanone conversion occurred in three steps which are protonation, cyclization, and then tautomerization. Based on these calculations, the rate determining step was the tautomerization reaction, which exhibited the same results with or without the solvent effects. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

 

Fulltext View|Download
Keywords: DFT; Reaction Mechanism; Chalcone Conversion; PCM Models; M06-2X
Funding: LPDP, Ministry of Finance, Republic of Indonesia under contract 20160721028063

Article Metrics:

Article Info
Section: Original Research Articles
Language : EN
Recent articles
Degradation of Ciprofloxacin by Titanium Dioxide (TiO2) Nanoparticles: Optimization of Conditions, Toxicity, and Degradation Pathway Reaction Kinetics of Levulinic Acid Synthesis from Glucose Using Bronsted Acid Catalyst Simultaneous Photocatalytic Esterification and Addition Reaction of Fatty Acids in Kemiri Sunan (Reutealis trisperma sp.) Oil over CuO/TiO2 Catalyst - A Novel Approach Backmatter (Publication Ethics, Copyright Transfer Agreement for Publishing Form) Frontmatter (Front Cover, Editorial Team, Indexing, and Table of Contents) More recent articles
  1. Taylor, L.P., Grotewold, E. (2005). Flavonoids as Developmental Regulators. Current Opinion in Biology, 8, 317-323. DOI: 10.1016/j.pbi.2005.03.005
  2. Cuyckens, F., Claeys, M. (2004). Mass Spectrometry in The Structural Analysis of Flavonoids. Journal of Mass Spectroscopy, 39, 1-15. DOI: 10.1002/jms.585
  3. Jez, J.M., Noel, J.P. (2002). Reaction Mechanism of Chalcone Isomerase. The Journal of Biological Chemistry, 277, 1361-1369. DOI: 10.1074/jbc.M109224200
  4. Mondal, R., Gupta, A.D., Malik, A.K. (2011). Synthesis of Flavanones by Use of Anhydrous Potassium Carbonate as An Inexpensive, Safe, and Efficient Basic Catalyst. Tetrahedron Letters, 52, 5020-5024. DOI: 10.1016/j.tetlet.2011.07.072
  5. Zang, Y., Wang, Y. (2014). Enantioselective Biomimetic Cyclization of 2’-Hydroxychalcones to Flavanones. Tetrahedron Letters, 55, 3255-3258. DOI: 10.1016/j.tetlet.2014.04.032
  6. Bhatti, H.A., Uddin, N., Ayub, K., Saima, B., Uroos, M., Iqbal, J., Anjum, S., Light, M.E., Hameed, A., Khan, K.M. (2015). Synthesis Characterization of Flavone, Isoflavone, and 2,3-Dihydrobenzeofuran-3-Carboxylate and Density Functional Studies. European Journal of Chemistry, 6(3), 305-313. DOI: 10.5155/eurjchem.6.3.305-313.1268
  7. Albogami, A.S., Karama, U., Mousa, A.A., Khan, M., Al-Mazroa, S.A., Alkhathlan, A.Z. (2012). Simple and Efficient One Step Synthesis of Functionalized Flavanones and Chalcones. Oriental Journal of Chemistry, 28, 619-626. ISSN: 0970-020 X
  8. Kulkarni, P., Wagh, P., Zubaidha., P. (2012). An Improved and Eco-Friendly Method for the Synthesis of Flavanone by the Cyclization of 2’-Hydroxy Chalcone using Methane Sulphonic Acid as Catalyst. Chemistry Journal, 2, 106-110. ISSN: 2049-954X
  9. Dittmer, C., Raabe, G., Hintermann, L. (2007). Asymmetric Cyclization of 2’-Hydroxychalcones to Flavanones: Catalysis by Chiral Bronsted Acids and Bases. European Journal of Organic Chemistry, 5886-5898. DOI: 10.1002/ejoc.200700682
  10. Cramer, J.C. (2004). Essentials of Computational Chemistry, Theories and Models Second Edition. John Wiley & Sons, Ltd
  11. Cheong, P.H., Legault, C.Y., Um, J.M., Celebi-Olcum, N., Houk, K.N. (2011). Quantum Mechanical Investigations of Organocatalysis: Mechanisms, Reactivities, and Selectivities. Chemical Review, 111, 5042-5137. DOI: 10.1021/cr100212h
  12. Gaussian 09, Revision D.01, Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M. , Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A., Peralta, Jr., J. E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Keith, T., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, O., Foresman, J.B., Ortiz, J.V., Cioslowski, J., Fox, D.J., Gaussian, Inc., Wallingford CT, 2013
  13. Nielsen, A.B., Holder, A.J. (2009). Gauss View 5.0, User’s Reference. GAUSSIAN Inc., Pittsburgh
  14. Chemcraft - graphical software for visualization of quantum chemistry computations. https://www.chemcraftprog.com
  15. Jmol: an open-source Java viewer for chemical structures in 3D. http://www.jmol.org/
  16. Lewars, E. G. (2011). Computational Chemistry : Introduction to the Theory and Applications of Molecular and Quantum Mechanics, 2nd Edition. Springer Science+Business Media
  17. Zhao, Y., Truhlar, D.G. (2008). The M06 Suite Of Density Functionals For Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, And Transition Elements: Two New Functionals And Systematic Testing Of Four M06-Class Functionals And 12 Other Functionals. Theoretical Chemistry Account, 120, 215-241. DOI: 10.1007/s00214-007-0310-x
  18. Cagardova, D., Michalik, M, Klein, E., Lukes, V., Marcovic, A. (2019). DFT And Ab Initio Calculations Of Ionization Potentials, Proton Affinities And Bond Dissociation Enthalpies Of Aromatic Compounds. Acta Chimica Slovaca, 12, 225-240. DOI: 10.2478/acs-2019-0032
  19. Wong, M.W., Gill, P.M.W., Nobes, R.H., Radom, L. (1988). 6-311G(MC) (d,p): A Second Row Analogue of the 6-31IG(d,p) Basis Set. Calculated Heats of Formation for Second-Row Hydrides. Journal of Physical Chemistry, 92, 4875-4880
  20. Hariharan, P.C., Pople, J.A. (1973). The Influence of Polarization Functions on Molecular Orbital Hydrogenation Energies. Theoretical Chimica Acta, 28, 213-222
  21. Mennucci, B., Tomasi, J., Cammi, R., Cheeseman, J.R., Frisch, M.J., Devlin, F.J., Gabriel, S., Stephens, P.J. (2002). Polarizable Continuum Model (PCM) Calculations of Solvent Effects on Optical Rotations of Chiral Molecules. Journal of Physical Chemistry A, 106(25), 6102-6113. DOI: 10.1021/jp020124t
  22. Gasque, L., Álvarez-Idaboy, J.R., Flores-Álamo, M., Guzmán-Méndez, Ó., Campos-Cerón, J.M. (2018). Theoretical and Experimental Study Demonstrates Kinetic Control in Chalconeflavanone Transformation of Naphthalene Derivatives. Journal of Molecular Structure, 1157, 631-637. DOI: 10.1016/j.molstruc.2017.12.078

Last update:

No citation recorded.

Last update:

No citation recorded.