3-Oxo-1,3-oxathiolanes-synthesis and stereochemistry

Kalevi Pihlaja, Jari Sinkkonen, G. Stájer

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The compound 3-oxo-1,3-oxathiolane (6) and its cis- and trans-2-methyl (7,8), 4-methyl (9,10), 5-methyl (11,12) and 2-p-nitrophenyl (13,14) derivatives were prepared by oxidizing the corresponding 1,3-oxathiolanes (1-5) with NalO4 in water. The oxides were purified and their isomers separated using thin layer chromatography. The structural characterization was carried out with 1H NMR spectroscopy and molecular modeling. Compounds 8-10,12, and 14 attain the half-chair type conformation with O(1) above and C(S) below the plane (HC1), but 6, 7, 11, and 13 are, for steric reasons, the mixtures with the alternative half-chair (HC2), where O(1) is below and C(5) above this plane. Accordingly, 6 appears based on the values of experimental coupling constants as an 81:19, 7 as a 37:63, 11 as a 33:67 and 13 as a 54:46 mixture of HC1 and HC2, respectively. The relative energies of these conformations, the values of the vicinal H,H-coupling constants and 1H chemical shifts were estimated for compounds 6-12 also by computational methods and they support nicely the conclusions based on experimental data.

Original languageEnglish
Pages (from-to)244-249
Number of pages6
JournalMagnetic Resonance in Chemistry
Volume46
Issue number3
DOIs
Publication statusPublished - Mar 2008

Fingerprint

Stereochemistry
stereochemistry
seats
Conformations
thin layer chromatography
Thin layer chromatography
Molecular modeling
Chemical shift
synthesis
Thin Layer Chromatography
Computational methods
Isomers
Oxides
Nuclear magnetic resonance spectroscopy
chemical equilibrium
Magnetic Resonance Spectroscopy
isomers
Derivatives
nuclear magnetic resonance
oxides

Keywords

  • 1H
  • 3-Oxo-1,3-oxathiolanes
  • DFT calculations
  • NMR
  • Stereochemistry

ASJC Scopus subject areas

  • Chemistry(all)
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Medicine(all)

Cite this

3-Oxo-1,3-oxathiolanes-synthesis and stereochemistry. / Pihlaja, Kalevi; Sinkkonen, Jari; Stájer, G.

In: Magnetic Resonance in Chemistry, Vol. 46, No. 3, 03.2008, p. 244-249.

Research output: Contribution to journalArticle

Pihlaja, Kalevi ; Sinkkonen, Jari ; Stájer, G. / 3-Oxo-1,3-oxathiolanes-synthesis and stereochemistry. In: Magnetic Resonance in Chemistry. 2008 ; Vol. 46, No. 3. pp. 244-249.
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