Conformational analysis of thiolane-1-amides: an x-ray study of thiolane-1-tosylimide and diastereoisomeric 2-alkylthiolane-1-(arylsulphonyl)imides
Identifieur interne : 003A97 ( Main/Exploration ); précédent : 003A96; suivant : 003A98Conformational analysis of thiolane-1-amides: an x-ray study of thiolane-1-tosylimide and diastereoisomeric 2-alkylthiolane-1-(arylsulphonyl)imides
Auteurs : I. Jalsovszky [Hongrie] ; Á. Kucsman [Hongrie] ; F. Ruff [Hongrie] ; Gy. Argay [Hongrie] ; T. Koritsánszky [Hongrie] ; A. Kálmán [Hongrie]Source :
- Journal of Molecular Structure [ 0022-2860 ] ; 1986.
Abstract
The molecular structures of thiolane-, trans-2-methylthiolane-, trans-2-ethylthiolane- and cis-2-tert-butylthiolane-1-tosylimide and that of cis-2-methylthiolane-1-(p-nitro-phenylsulphonyl)imide were investigated by X-ray diffraction. The results confirmed our earlier 13C-NMR assignments of configurations. Direct evidence was obtained for ring geometry and conformational preference of ring substituents and cyclic sulphilimines were compared with analogous sulphoxides and sulphonium salts. It has been found that the electron-withdrawing and bulky NTs (N-tosyl) group is pseudoaxial in thiolane-1-tosylimide. The conformations of 1,2-disubstituted thiolanes are controlled by steric repulsion between 1-(arylsulphonyl)imino and 2-alkyl groups, which are 1-axial and 2-equatorial in cis derivatives, and 1-endo-isoclina and 2-exo-isoclinal in trans isomers. The 2-tert-butyl group and C4/C5 ring atoms are almost antiperiplanar. In connection with the conformation of the S-tosylimino part, rotations about SIVN, NSVI and SVICar bonds are analysed, and deviations from a SIV-symmetric conformation and “Koch-Moffitt's case IIa of conjugation” are interpreted in terms of steric and stereoelectronic effects. Changes in SIVC, SVIN and SVIO bond lengths are also rationalized.
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DOI: 10.1016/0022-2860(87)87024-2
Affiliations:
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Jalsovszky</name><affiliation wicri:level="1"><country xml:lang="fr">Hongrie</country><wicri:regionArea>Institute of Organic Chemistry, L. Eötvös University, P.O. Box 325</wicri:regionArea><wicri:noRegion>P.O. Box 325</wicri:noRegion></affiliation></author><author><name sortKey="Kucsman, A" sort="Kucsman, A" uniqKey="Kucsman A" first="Á." last="Kucsman">Á. Kucsman</name><affiliation wicri:level="1"><country xml:lang="fr">Hongrie</country><wicri:regionArea>Institute of Organic Chemistry, L. Eötvös University, P.O. Box 325</wicri:regionArea><wicri:noRegion>P.O. Box 325</wicri:noRegion></affiliation></author><author><name sortKey="Ruff, F" sort="Ruff, F" uniqKey="Ruff F" first="F." last="Ruff">F. Ruff</name><affiliation wicri:level="1"><country xml:lang="fr">Hongrie</country><wicri:regionArea>Institute of Organic Chemistry, L. Eötvös University, P.O. Box 325</wicri:regionArea><wicri:noRegion>P.O. Box 325</wicri:noRegion></affiliation></author><author><name sortKey="Argay, Gy" sort="Argay, Gy" uniqKey="Argay G" first="Gy." last="Argay">Gy. Argay</name><affiliation wicri:level="1"><country xml:lang="fr">Hongrie</country><wicri:regionArea>Central Research Institute of Chemistry, Hungarian Academy of Sciences, P.O. Box 17</wicri:regionArea><wicri:noRegion>P.O. Box 17</wicri:noRegion></affiliation></author><author><name sortKey="Koritsanszky, T" sort="Koritsanszky, T" uniqKey="Koritsanszky T" first="T." last="Koritsánszky">T. Koritsánszky</name><affiliation wicri:level="1"><country xml:lang="fr">Hongrie</country><wicri:regionArea>Central Research Institute of Chemistry, Hungarian Academy of Sciences, P.O. Box 17</wicri:regionArea><wicri:noRegion>P.O. Box 17</wicri:noRegion></affiliation></author><author><name sortKey="Kalman, A" sort="Kalman, A" uniqKey="Kalman A" first="A." last="Kálmán">A. Kálmán</name><affiliation wicri:level="1"><country xml:lang="fr">Hongrie</country><wicri:regionArea>Central Research Institute of Chemistry, Hungarian Academy of Sciences, P.O. Box 17</wicri:regionArea><wicri:noRegion>P.O. Box 17</wicri:noRegion></affiliation></author></analytic><monogr></monogr><series><title level="j">Journal of Molecular Structure</title><title level="j" type="abbrev">MOLSTR</title><idno type="ISSN">0022-2860</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1986">1986</date><biblScope unit="volume">156</biblScope><biblScope unit="issue">3–4</biblScope><biblScope unit="page" from="193">193</biblScope><biblScope unit="page" to="212">212</biblScope></imprint><idno type="ISSN">0022-2860</idno></series><idno type="istex">06B5DEE61E462AE4BDB70960FEC3E6952E3E02FE</idno><idno type="DOI">10.1016/0022-2860(87)87024-2</idno><idno type="PII">0022-2860(87)87024-2</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0022-2860</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The molecular structures of thiolane-, trans-2-methylthiolane-, trans-2-ethylthiolane- and cis-2-tert-butylthiolane-1-tosylimide and that of cis-2-methylthiolane-1-(p-nitro-phenylsulphonyl)imide were investigated by X-ray diffraction. The results confirmed our earlier 13C-NMR assignments of configurations. Direct evidence was obtained for ring geometry and conformational preference of ring substituents and cyclic sulphilimines were compared with analogous sulphoxides and sulphonium salts. It has been found that the electron-withdrawing and bulky NTs (N-tosyl) group is pseudoaxial in thiolane-1-tosylimide. The conformations of 1,2-disubstituted thiolanes are controlled by steric repulsion between 1-(arylsulphonyl)imino and 2-alkyl groups, which are 1-axial and 2-equatorial in cis derivatives, and 1-endo-isoclina and 2-exo-isoclinal in trans isomers. The 2-tert-butyl group and C4/C5 ring atoms are almost antiperiplanar. In connection with the conformation of the S-tosylimino part, rotations about SIVN, NSVI and SVICar bonds are analysed, and deviations from a SIV-symmetric conformation and “Koch-Moffitt's case IIa of conjugation” are interpreted in terms of steric and stereoelectronic effects. Changes in SIVC, SVIN and SVIO bond lengths are also rationalized.</div></front></TEI><affiliations><list><country><li>Hongrie</li></country></list><tree><country name="Hongrie"><noRegion><name sortKey="Jalsovszky, I" sort="Jalsovszky, I" uniqKey="Jalsovszky I" first="I." last="Jalsovszky">I. Jalsovszky</name></noRegion><name sortKey="Argay, Gy" sort="Argay, Gy" uniqKey="Argay G" first="Gy." last="Argay">Gy. Argay</name><name sortKey="Kalman, A" sort="Kalman, A" uniqKey="Kalman A" first="A." last="Kálmán">A. Kálmán</name><name sortKey="Koritsanszky, T" sort="Koritsanszky, T" uniqKey="Koritsanszky T" first="T." last="Koritsánszky">T. Koritsánszky</name><name sortKey="Kucsman, A" sort="Kucsman, A" uniqKey="Kucsman A" first="Á." last="Kucsman">Á. Kucsman</name><name sortKey="Ruff, F" sort="Ruff, F" uniqKey="Ruff F" first="F." last="Ruff">F. Ruff</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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