1H, 13C, 17O NMR and quantum-chemical study of the stereochemistry of the sulfoxide and sulfone derivatives of 3-arylidene-1-thioflavan-4-one epoxides

József Kovács, Gábor Tóth, András Simon, Albert Lévai, Andreas Koch, Erich Kleinpeter

Research output: Article

42 Citations (Scopus)

Abstract

The oxidation of the trans,cis-(2) and trans,trans-epoxides (3) of differently substituted (Z)-3-arylidene-1-thioflavan-4-ones (1) with dimethyldioxirane (DMD) yielded the appropriate sulfoxides (4, 5) and sulfones (6, 7). The structures were elucidated by the extensive application of one- and two-dimensional 1H, 13C and 17O NMR spectroscopy. The conformational analysis was achieved by the application of 3J(C,H) coupling constants, NOESY responses and ab initio calculations. The preferred ground-state conformers (twisted envelope-A, twisted envelope-B for 6 and twisted envelope-A, envelope-B for 7) were obtained as global minima of the theoretical ab initio MO study and also the examination of the 17O and 13C chemical shifts, calculated for the global minima structures of the sulfone isomers by the GIAO method. Analogous results, obtained for the sulfoxide isomers (4, 5), not only led to the preferred conformers but also gave evidence for the trans arrangement of the 2-Ph group and the oxygen atom of the S=O group. Chemical shift differences between the isomers, sulfoxides and sulfones were corroborated by ab initio calculations of the anisotropic effects of the oxirane ring and the S=O and SO2 groups.

Original languageEnglish
Pages (from-to)193-201
Number of pages9
JournalMagnetic Resonance in Chemistry
Volume41
Issue number3
DOIs
Publication statusPublished - márc. 1 2003

Fingerprint

sulfoxide
Sulfones
Stereochemistry
sulfones
epoxy compounds
Epoxy Compounds
stereochemistry
Isomers
Sulfoxides
envelopes
Nuclear magnetic resonance
Chemical shift
Derivatives
nuclear magnetic resonance
isomers
chemical equilibrium
Ethylene Oxide
Ground state
Nuclear magnetic resonance spectroscopy
Oxygen

ASJC Scopus subject areas

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

Cite this

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title = "1H, 13C, 17O NMR and quantum-chemical study of the stereochemistry of the sulfoxide and sulfone derivatives of 3-arylidene-1-thioflavan-4-one epoxides",
abstract = "The oxidation of the trans,cis-(2) and trans,trans-epoxides (3) of differently substituted (Z)-3-arylidene-1-thioflavan-4-ones (1) with dimethyldioxirane (DMD) yielded the appropriate sulfoxides (4, 5) and sulfones (6, 7). The structures were elucidated by the extensive application of one- and two-dimensional 1H, 13C and 17O NMR spectroscopy. The conformational analysis was achieved by the application of 3J(C,H) coupling constants, NOESY responses and ab initio calculations. The preferred ground-state conformers (twisted envelope-A, twisted envelope-B for 6 and twisted envelope-A, envelope-B for 7) were obtained as global minima of the theoretical ab initio MO study and also the examination of the 17O and 13C chemical shifts, calculated for the global minima structures of the sulfone isomers by the GIAO method. Analogous results, obtained for the sulfoxide isomers (4, 5), not only led to the preferred conformers but also gave evidence for the trans arrangement of the 2-Ph group and the oxygen atom of the S=O group. Chemical shift differences between the isomers, sulfoxides and sulfones were corroborated by ab initio calculations of the anisotropic effects of the oxirane ring and the S=O and SO2 groups.",
keywords = "C NMR, O NMR, H NMR, J(C,H) couplings, B3LYP/6-31G* DFT calculation, Conformational analysis, NMR, Spiroepoxides",
author = "J{\'o}zsef Kov{\'a}cs and G{\'a}bor T{\'o}th and Andr{\'a}s Simon and Albert L{\'e}vai and Andreas Koch and Erich Kleinpeter",
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TY - JOUR

T1 - 1H, 13C, 17O NMR and quantum-chemical study of the stereochemistry of the sulfoxide and sulfone derivatives of 3-arylidene-1-thioflavan-4-one epoxides

AU - Kovács, József

AU - Tóth, Gábor

AU - Simon, András

AU - Lévai, Albert

AU - Koch, Andreas

AU - Kleinpeter, Erich

PY - 2003/3/1

Y1 - 2003/3/1

N2 - The oxidation of the trans,cis-(2) and trans,trans-epoxides (3) of differently substituted (Z)-3-arylidene-1-thioflavan-4-ones (1) with dimethyldioxirane (DMD) yielded the appropriate sulfoxides (4, 5) and sulfones (6, 7). The structures were elucidated by the extensive application of one- and two-dimensional 1H, 13C and 17O NMR spectroscopy. The conformational analysis was achieved by the application of 3J(C,H) coupling constants, NOESY responses and ab initio calculations. The preferred ground-state conformers (twisted envelope-A, twisted envelope-B for 6 and twisted envelope-A, envelope-B for 7) were obtained as global minima of the theoretical ab initio MO study and also the examination of the 17O and 13C chemical shifts, calculated for the global minima structures of the sulfone isomers by the GIAO method. Analogous results, obtained for the sulfoxide isomers (4, 5), not only led to the preferred conformers but also gave evidence for the trans arrangement of the 2-Ph group and the oxygen atom of the S=O group. Chemical shift differences between the isomers, sulfoxides and sulfones were corroborated by ab initio calculations of the anisotropic effects of the oxirane ring and the S=O and SO2 groups.

AB - The oxidation of the trans,cis-(2) and trans,trans-epoxides (3) of differently substituted (Z)-3-arylidene-1-thioflavan-4-ones (1) with dimethyldioxirane (DMD) yielded the appropriate sulfoxides (4, 5) and sulfones (6, 7). The structures were elucidated by the extensive application of one- and two-dimensional 1H, 13C and 17O NMR spectroscopy. The conformational analysis was achieved by the application of 3J(C,H) coupling constants, NOESY responses and ab initio calculations. The preferred ground-state conformers (twisted envelope-A, twisted envelope-B for 6 and twisted envelope-A, envelope-B for 7) were obtained as global minima of the theoretical ab initio MO study and also the examination of the 17O and 13C chemical shifts, calculated for the global minima structures of the sulfone isomers by the GIAO method. Analogous results, obtained for the sulfoxide isomers (4, 5), not only led to the preferred conformers but also gave evidence for the trans arrangement of the 2-Ph group and the oxygen atom of the S=O group. Chemical shift differences between the isomers, sulfoxides and sulfones were corroborated by ab initio calculations of the anisotropic effects of the oxirane ring and the S=O and SO2 groups.

KW - C NMR

KW - O NMR

KW - H NMR

KW - J(C,H) couplings

KW - B3LYP/6-31G DFT calculation

KW - Conformational analysis

KW - NMR

KW - Spiroepoxides

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U2 - 10.1002/mrc.1153

DO - 10.1002/mrc.1153

M3 - Article

AN - SCOPUS:0037283319

VL - 41

SP - 193

EP - 201

JO - Magnetic Resonance in Chemistry

JF - Magnetic Resonance in Chemistry

SN - 0749-1581

IS - 3

ER -