Nuclear magnetic resonance signaling of molecular chiral information using an achiral reagent

Atsuomi Shundo, Jan Labuta, Jonathan P. Hill, Shinsuke Ishihara, Katsuhiko Ariga

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

(Figure Presented) Until now NMR spectroscopic detection of guest chirality using an achiral host has not been possible in the absence of a chiral medium or auxiliary since chiral discrimination is principally based on chiral discrimination by host and/or diastereomeric host-guest complex formation. In this paper, we demonstrate that an achiral oxoporphyrinogen works as a host capable of signaling chiral information of α-hydroxycarboxylic acids in 1H NMR spectroscopy. In particular, enantiomeric excess (ee) can be determined by observing the splitting of 1H NMR resonances of the achiral host. This differs from the case of chiral hosts (shift reagents) where % ee is generally determined from the ratio of peak areas due to diastereomeric host-guest complexes. UV/vis, CD, FT-IR, and NMR spectroscopic investigations suggest that the unusual phenomenon reported here is based on formation of a complex with 1:2 stoichiometry in concert with a protonation-driven tautomerization of the host.

Original languageEnglish
Pages (from-to)9494-9495
Number of pages2
JournalJournal of the American Chemical Society
Volume131
Issue number27
DOIs
Publication statusPublished - Jul 15 2009
Externally publishedYes

Fingerprint

Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
Chirality
Protonation
Stoichiometry
Nuclear magnetic resonance spectroscopy
Acids
Proton Magnetic Resonance Spectroscopy

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Nuclear magnetic resonance signaling of molecular chiral information using an achiral reagent. / Shundo, Atsuomi; Labuta, Jan; Hill, Jonathan P.; Ishihara, Shinsuke; Ariga, Katsuhiko.

In: Journal of the American Chemical Society, Vol. 131, No. 27, 15.07.2009, p. 9494-9495.

Research output: Contribution to journalArticle

Shundo, Atsuomi ; Labuta, Jan ; Hill, Jonathan P. ; Ishihara, Shinsuke ; Ariga, Katsuhiko. / Nuclear magnetic resonance signaling of molecular chiral information using an achiral reagent. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 27. pp. 9494-9495.
@article{e22cfcd4e4ec47ebaa6d47604d14879a,
title = "Nuclear magnetic resonance signaling of molecular chiral information using an achiral reagent",
abstract = "(Figure Presented) Until now NMR spectroscopic detection of guest chirality using an achiral host has not been possible in the absence of a chiral medium or auxiliary since chiral discrimination is principally based on chiral discrimination by host and/or diastereomeric host-guest complex formation. In this paper, we demonstrate that an achiral oxoporphyrinogen works as a host capable of signaling chiral information of α-hydroxycarboxylic acids in 1H NMR spectroscopy. In particular, enantiomeric excess (ee) can be determined by observing the splitting of 1H NMR resonances of the achiral host. This differs from the case of chiral hosts (shift reagents) where {\%} ee is generally determined from the ratio of peak areas due to diastereomeric host-guest complexes. UV/vis, CD, FT-IR, and NMR spectroscopic investigations suggest that the unusual phenomenon reported here is based on formation of a complex with 1:2 stoichiometry in concert with a protonation-driven tautomerization of the host.",
author = "Atsuomi Shundo and Jan Labuta and Hill, {Jonathan P.} and Shinsuke Ishihara and Katsuhiko Ariga",
year = "2009",
month = "7",
day = "15",
doi = "10.1021/ja903371d",
language = "English",
volume = "131",
pages = "9494--9495",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "27",

}

TY - JOUR

T1 - Nuclear magnetic resonance signaling of molecular chiral information using an achiral reagent

AU - Shundo, Atsuomi

AU - Labuta, Jan

AU - Hill, Jonathan P.

AU - Ishihara, Shinsuke

AU - Ariga, Katsuhiko

PY - 2009/7/15

Y1 - 2009/7/15

N2 - (Figure Presented) Until now NMR spectroscopic detection of guest chirality using an achiral host has not been possible in the absence of a chiral medium or auxiliary since chiral discrimination is principally based on chiral discrimination by host and/or diastereomeric host-guest complex formation. In this paper, we demonstrate that an achiral oxoporphyrinogen works as a host capable of signaling chiral information of α-hydroxycarboxylic acids in 1H NMR spectroscopy. In particular, enantiomeric excess (ee) can be determined by observing the splitting of 1H NMR resonances of the achiral host. This differs from the case of chiral hosts (shift reagents) where % ee is generally determined from the ratio of peak areas due to diastereomeric host-guest complexes. UV/vis, CD, FT-IR, and NMR spectroscopic investigations suggest that the unusual phenomenon reported here is based on formation of a complex with 1:2 stoichiometry in concert with a protonation-driven tautomerization of the host.

AB - (Figure Presented) Until now NMR spectroscopic detection of guest chirality using an achiral host has not been possible in the absence of a chiral medium or auxiliary since chiral discrimination is principally based on chiral discrimination by host and/or diastereomeric host-guest complex formation. In this paper, we demonstrate that an achiral oxoporphyrinogen works as a host capable of signaling chiral information of α-hydroxycarboxylic acids in 1H NMR spectroscopy. In particular, enantiomeric excess (ee) can be determined by observing the splitting of 1H NMR resonances of the achiral host. This differs from the case of chiral hosts (shift reagents) where % ee is generally determined from the ratio of peak areas due to diastereomeric host-guest complexes. UV/vis, CD, FT-IR, and NMR spectroscopic investigations suggest that the unusual phenomenon reported here is based on formation of a complex with 1:2 stoichiometry in concert with a protonation-driven tautomerization of the host.

UR - http://www.scopus.com/inward/record.url?scp=67650495495&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=67650495495&partnerID=8YFLogxK

U2 - 10.1021/ja903371d

DO - 10.1021/ja903371d

M3 - Article

C2 - 19545158

AN - SCOPUS:67650495495

VL - 131

SP - 9494

EP - 9495

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 27

ER -