Jump to main content
Jump to site search

Issue 16, 2013
Previous Article Next Article

Impact of long-range van der Waals forces on chiral recognition in a Cinchona alkaloid chiral selector system

Author affiliations

Abstract

Singly-charged complexes of (8S,9R)-tert-butylcarbamoylquinine (tBuCQN), N-3,5-dinitrobenzoyl-(S,R)-leucine (DNB-S/R-leucine), and alkali metal counter ions (Li+, Na+, K+) were investigated by density-functional theory. It is shown that the cations prefer formation of an ionic pair with the carboxylate group of DNB-Leu over the formation of a cation–π interaction. The [tBuCQN·DNB-S/R-Leu·Na]+ complex is bound by a Coulombic attraction, a hydrogen bond, a π−π interaction and van der Waals forces. The tBuCQN chiral selector preferentially complexes with the DNB-S-Leu enantiomer, because the favourable stereochemistry allows the stabilization of the complex by at least one binding mode more compared to the complex containing the DNB-R-Leu molecule. Weakening of the binding modes is observed using the lithium counter ion compared to the sodium one. The weakening is more pronounced in [tBuCQN·DNB-R-Leu·Li]+ than in [tBuCQN·DNB-S-Leu·Li]+. The exact opposite effect is observed using the potassium counter ion. Hence, the lithium counter ion enhances the enantioselectivity of tBuCQN while the potassium counter ion reduces the enantioselectivity of tBuCQN.

Graphical abstract: Impact of long-range van der Waals forces on chiral recognition in a Cinchona alkaloid chiral selector system

Back to tab navigation

Supplementary files

Publication details

The article was received on 10 Dec 2012, accepted on 25 Feb 2013 and first published on 18 Mar 2013


Article type: Paper
DOI: 10.1039/C3CP44444A
Phys. Chem. Chem. Phys., 2013,15, 6113-6121
  • Open access: Creative Commons BY license
  •   Request permissions

    Impact of long-range van der Waals forces on chiral recognition in a Cinchona alkaloid chiral selector system

    P. Milko, J. Roithová, K. A. Schug and K. Lemr, Phys. Chem. Chem. Phys., 2013, 15, 6113
    DOI: 10.1039/C3CP44444A

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements