1-oxo-1,3-dithiolanes-synthesis and stereochemistry

Kalevi Pihlaja, Jari Sinkkonen, Gezá Stájer, Andreas Koch, Erich Kleinpeter

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3 Citations (Scopus)

Abstract

1-Oxo-1,3-dithiolane (4) and its cis- and trans-2-methyl (5,6), -4-methyl (7,8) and -5-methyl (9,10) derivatives were prepared by oxidizing the corresponding 1,3-dithiolanes (1-3) with NaIO4 in water. The oxides were purified and their isomers separated using thin layer chromatography. The structural characterization was carried out with 1H and 13C NMR spectroscopy and molecular modelling. The sulfoxides 4-6 and 8-10 attain two S(1) type envelopes (sometimes slightly distorted) the S=O ax envelope greatly dominating. Cis-4-methyl-1-oxo-1,3-dithiolane is a special case exhibiting both two closely related S=Oax (30 and 27%) as well as S=Oeq (21 and 22%) forms [S(1) and C(4) envelopes, respectively]. The relative energies of these conformations, the values of 1H-1H coupling constants and 1H and 13C chemical shifts were estimated by computational methods and they support well the conclusions based on the experimental data.

Original languageEnglish
Pages (from-to)443-449
Number of pages7
JournalMagnetic Resonance in Chemistry
Volume49
Issue number7
DOIs
Publication statusPublished - Jul 1 2011

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Keywords

  • C NMR
  • H NMR
  • NMR
  • computational chemistry
  • conformational analysis
  • sulfur heterocycles

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)

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