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Nieminen V, Murzin DY, Klika KD. NMR and molecular modeling of the dimeric self-association of the enantiomers of 1,1'-bi-2-naphthol and 1-phenyl-2,2,2-trifluoroethanol in the solution state and their relevance to enantiomer self-disproportionation on achiral-phase chromatography (ESDAC). Org Biomol Chem. 2008;7(3):537-42doi: 10.1039/b814905d.
Nieminen, V., Murzin, D. Y., & Klika, K. D. (2009). NMR and molecular modeling of the dimeric self-association of the enantiomers of 1,1'-bi-2-naphthol and 1-phenyl-2,2,2-trifluoroethanol in the solution state and their relevance to enantiomer self-disproportionation on achiral-phase chromatography (ESDAC). Organic & biomolecular chemistry, 7(3), 537-42. https://doi.org/10.1039/b814905d
Nieminen, Ville, et al. "NMR and molecular modeling of the dimeric self-association of the enantiomers of 1,1'-bi-2-naphthol and 1-phenyl-2,2,2-trifluoroethanol in the solution state and their relevance to enantiomer self-disproportionation on achiral-phase chromatography (ESDAC)." Organic & biomolecular chemistry vol. 7,3 (2009): 537-42. doi: https://doi.org/10.1039/b814905d
Nieminen V, Murzin DY, Klika KD. NMR and molecular modeling of the dimeric self-association of the enantiomers of 1,1'-bi-2-naphthol and 1-phenyl-2,2,2-trifluoroethanol in the solution state and their relevance to enantiomer self-disproportionation on achiral-phase chromatography (ESDAC). Org Biomol Chem. 2009 Feb 07;7(3):537-42. doi: 10.1039/b814905d. Epub 2008 Nov 26. PMID: 19156320.
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Org Biomol Chem. 2009 Feb 07;7(3):537-42. doi: 10.1039/b814905d. Epub 2008 Nov 26.

NMR and molecular modeling of the dimeric self-association of the enantiomers of 1,1'-bi-2-naphthol and 1-phenyl-2,2,2-trifluoroethanol in the solution state and their relevance to enantiomer self-disproportionation on achiral-phase chromatography (ESDAC).

Organic & biomolecular chemistry

Ville Nieminen, Dmitry Yu Murzin, Karel D Klika

Affiliations

  1. Laboratory of Industrial Chemistry, Process Chemistry Centre, Abo Akademi University, FIN-20500 Abo, Finland.

PMID: 19156320 DOI: 10.1039/b814905d

Abstract

Molecular modeling of the homo- and heterochiral dimeric self-associates of the enantiomers of 1,1'-bi-2-naphthol and 1-phenyl-2,2,2-trifluoroethanol in solution has been performed in order to understand their NMR behavior and in light of the phenomenon of "enantiomer self-disproportionation on achiral-phase chromatography" (ESDAC). For 1,1'-bi-2-naphthol in C(6)D(6), distinct NMR signals for each enantiomer arise for some spins in non-racemic mixtures-the phenomenon of self-induced diastereomeric anisochronism (SIDA). The linear divergence of these split signals across an enantiomeric titration (a series of samples in which the percentage of one enantiomer is varied from 50-100% whilst maintaining a constant total concentration), as well as the near linear migration of certain signals in CDCl(3) across a similar enantiomeric titration, where signals were not observed to be split, is consistent with the calculated small energy differences between the homo- and heterochiral associates. For an enantiomeric titration of 1-phenyl-2,2,2-trifluoroethanol in n-hexane, NMR signals also remained unsplit but the noticeable migration of some revealed a skew indicative of a preference for the heterochiral associate. This was duly reflected in the calculations which provided a DeltaG value favoring the heterochiral associate by 2.4 kJ mol(-1). The relevance of these results to evaluating the likely occurrence of ESDAC is considered.

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