1-Oxo-1,3-dithiolanesùsynthesis and stereochemistry
- 1-Oxo-1,3-dithiolane (4) and its cis- andtrans-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=Oax 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.
Author details: | Erich KleinpeterORCiDGND, Kalevi Pihlaja, Jari Sinkkonen, Gezá Stájer, Andreas KochORCiDGND |
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ISSN: | 0749-1581 |
Publication type: | Article |
Language: | English |
Year of first publication: | 2011 |
Publication year: | 2011 |
Release date: | 2017/03/25 |
Source: | Magnetic resonance in chemistry. - ISSN 0749-1581. - 49 (2011), S. 443 - 449 |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |