Ab initio Study of Chiral Recognition of β-Butyrolactone by Cyclodextrins

  • Waraporn Parasuk
  • Vudhichai Parasuk
Part of the Lecture Notes in Computer Science book series (LNCS, volume 3993)


Separation of stereoisomers of organic compounds is an important and challenge task for chemists. Cyclodextrins and their derivatives have been widely used in chromatography for this application. Experimental results indicated that substituents on the hydroxyl groups of cyclodextrin affect the efficiency of the chiral separation of β-butyrolactone. The understanding of the interactions contributed to the chiral recognition of cyclodextrin would help us predict the separation capability of a specific pair of cyclodextrin and chiral compound. Thus, the cyclodextrin substituent effect on the chiral recognition should be systematically investigated. In this study, Hartree Fock method with 3-21G basis set and density functional theory B3LYP with 6-31G* basis set were applied to determine the chiral recognition of a chiral model, β- butyrolactone, by β-cyclodextrin and its derivatives. Both methods predicted comparable values of chiral recognition of β-cyclodextrin derivatives. We found that methoxyl substitution on the wider rim of cyclodextrin (secondary hydroxyl groups) give the most effective chiral separation (ΔΔE=18.2 kcal/mol in favor of R-isomer) followed by substitution on the narrow rim (ΔΔE=9.5 kcal/mol in favor of S-isomer) while substitution on both side give the worst recognition (ΔΔE=3.2 kcal/mol in favor of S-isomer). This suggests that β-cyclodextrin with substitution only on the wider rim give the best chiral selectivity. By replacing methyl group with chiral hydroxypropyl group, we found that the chiral selectivity is reduced (ΔΔE=6.4 and 8.4 kcal/mol respectively for R- and S-form of hydroxypropyl group). This implies that the bulky group causes the reduction of the chiral selectivity.


Inclusion Complex Chiral Selectivity Chiral Separation Chiral Recognition Cyclodextrin Derivative 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


  1. 1.
    Li, S., Purdy, W.C.: Cyclodextrins and Their Applications in Analytical Chemistry. Chem. Rev. 92, 1457–1470 (1992)CrossRefGoogle Scholar
  2. 2.
    Lipkowitz, K.B., Pearl, G., Coner, B., Peterson, M.A.: Explanation of Where and How Enantioselective Binding Takes Place on Permethylated β-Cyclodextrin, a Chiral Stationary Phase used in Gas Chromatography. J. Am. Chem. Soc. 119, 600–610 (1997)CrossRefGoogle Scholar
  3. 3.
    Armstrong, D.W., Li, W., Chang, C.-D., Pitha, J.: Polar-liquid, Derivatized Cyclodextrin Stationary Phases for the Capillary Gas Chromatography Separation of Enantiomers. Anal. Chem. 62, 914–923 (1990)CrossRefGoogle Scholar
  4. 4.
    Schurig, V., Nowotny, H.-P.: Gas Chromatographic Separation of Enantiomers on Cyclodextrin Derivatives. Angew. Chem. Int. Ed. Engl. 29, 939–957 (1990)CrossRefGoogle Scholar
  5. 5.
    Armstrong, D.W., Ward, T.J., Armstrong, R.D., Beesley, T.E.: Separation of Drug Stereoisomers by the Formation of β-Cyclodextrin Inclusion Complexes. Science 232, 1132–1135 (1986)CrossRefGoogle Scholar
  6. 6.
    Shitangkoon, A., Vigh, G.: Gas Chromatographic Enantiomer Separations using Chloroacylpentyl Cyclodextrins. In: Abstracts of the 24th Congress on Science and Technology of Thailand, Bangkok, pp. 218–219 (1998)Google Scholar
  7. 7.
    Parasuk, W., Longwan, N., Tasanakosol, W.: Enantiomer Recognition of of β-Butyrolactone by Cyclodextrin. In: The fifth Annual National Symposium on Computational Science and Engineering, Bangkok, pp. 187–193 (2001)Google Scholar
  8. 8.
    Gaussian 98, Revision A9, Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Montgomery Jr., J.A., Stratmann, R.E., Burant, J.C., Dapprich, S., Millam, J.M., Daniels, A.D., Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J., Barone, V., Cossi, M., Cammi, R., Mennucci, B., Pomelli, C., Adamo, C., Clifford, S., Ochterski, J., Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Cioslowski, J., Ortiz, J.V., Baboul, A.G., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Gomperts, R., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M. W., Andres, J.L., Gonzalez, C., Head-Gordon, M., Replogle, E.S., Pople, J.A.: Gaussian, Inc., Pittsburgh, PA (1998)Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2006

Authors and Affiliations

  • Waraporn Parasuk
    • 1
  • Vudhichai Parasuk
    • 2
  1. 1.Department of Chemistry, Faculty of ScienceKasetsart UniversityBangkokThailand
  2. 2.Department of Chemistry, Faculty of ScienceChulalongkorn UniversityBangkokThailand

Personalised recommendations