NMR spectroscopic detection of chirality and enantiopurity in referenced systems without formation of diastereomers

Jan Labuta, Shinsuke Ishihara, Tomáš Šikorský, Zdeněk Futera, Atsuomi Shundo, Lenka Hanyková, Jaroslav V. Burda, Katsuhiko Ariga, Jonathan P. Hill

Research output: Contribution to journalArticle

55 Citations (Scopus)

Abstract

Enantiomeric excess of chiral compounds is a key parameter that determines their activity or therapeutic action. The current paradigm for rapid measurement of enantiomeric excess using NMR is based on the formation of diastereomeric complexes between the chiral analyte and a chiral resolving agent, leading to (at least) two species with no symmetry relationship. Here we report an effective method of enantiomeric excess determination using a symmetrical achiral molecule as the resolving agent, which is based on the complexation with analyte (in the fast exchange regime) without the formation of diastereomers. The use of N,N′-disubstituted oxoporphyrinogen as the resolving agent makes this novel method extremely versatile, and appropriate for various chiral analytes including carboxylic acids, esters, alcohols and protected amino acids using the same achiral molecule. The model of sensing mechanism exhibits a fundamental linear response between enantiomeric excess and the observed magnitude of induced chemical shift non-equivalence in the 1H NMR spectra.

Original languageEnglish
Article number2188
JournalNature communications
Volume4
DOIs
Publication statusPublished - Dec 1 2013

Fingerprint

Chirality
chirality
Nuclear magnetic resonance
nuclear magnetic resonance
Carboxylic Acids
Esters
Molecules
Alcohols
Chemical shift
Complexation
Amino Acids
carboxylic acids
amino acids
chemical equilibrium
esters
molecules
Ion exchange
alcohols
symmetry
Therapeutics

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

NMR spectroscopic detection of chirality and enantiopurity in referenced systems without formation of diastereomers. / Labuta, Jan; Ishihara, Shinsuke; Šikorský, Tomáš; Futera, Zdeněk; Shundo, Atsuomi; Hanyková, Lenka; Burda, Jaroslav V.; Ariga, Katsuhiko; Hill, Jonathan P.

In: Nature communications, Vol. 4, 2188, 01.12.2013.

Research output: Contribution to journalArticle

Labuta, J, Ishihara, S, Šikorský, T, Futera, Z, Shundo, A, Hanyková, L, Burda, JV, Ariga, K & Hill, JP 2013, 'NMR spectroscopic detection of chirality and enantiopurity in referenced systems without formation of diastereomers', Nature communications, vol. 4, 2188. https://doi.org/10.1038/ncomms3188
Labuta, Jan ; Ishihara, Shinsuke ; Šikorský, Tomáš ; Futera, Zdeněk ; Shundo, Atsuomi ; Hanyková, Lenka ; Burda, Jaroslav V. ; Ariga, Katsuhiko ; Hill, Jonathan P. / NMR spectroscopic detection of chirality and enantiopurity in referenced systems without formation of diastereomers. In: Nature communications. 2013 ; Vol. 4.
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