Stereochemistry of the formation and hydrolysis of a dithioether dication

Richard S Glass, Jeffrey L. Broeker, Habib Firouzabadi

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Abstract

Naphtho[1,8-bc]-1,5-dithiocin 1-oxide (7) was prepared by oxidation of naphtho[1,8-6c]-1,5-dithiocin with sodium metaperiodate in aqueous methanol. The structure and conformation of sulfoxide 7 in the solid state was unequivocally established to be boat 7A with equatorial sulfoxide by X-ray crystallographic analysis. Sulfoxide 7 crystallizes in the triclinic space group P1 (no. 2) with a = 8.959 (2), b = 11.313(3), and c = 12.975 (3) Å, α = 64.98 (2)°; β = 81.18 (2)°, γ = 78.67 (2)°, and Z = 4. The structure was solved by direct methods. Full-matrix least-squares refinement led to a conventional R factor of 0.040 after several cycles of anisotropic refinement. Dissolution of sulfoxide 7 in concentrated sulfuric acid produces disulfide dication 8, which on hydrolysis regenerates the sulfoxide. Deprotonation of sulfoxide 7 with methyllithium followed by treatment with D2O stereoselectively gives monodeuterated sulfoxide 7 (X = D). 1H NMR spectroscopic analysis of sulfoxide 7 (X = H) revealed that it is predominantly in chair conformation 7B with equatorial sulfoxide and the deuterium atom in the monodeuterated derivative is predominantly axial (7B, Ha = D). Disulfide dication 8 is deduced to be predominantly in boat conformation 8A by 1H NMR spectroscopic analysis and that derived from monodeuterated sulfoxide 7 has the deuterium predominantly axial (8A, Hb = D). Hydrolysis of the deuterated disulfide dication regenerates sulfoxide 7 with the deuterium axial. These surprising stereochemical results require retention of configuration at the sulfoxide sulfur both in the formation of disulfide dication 8 and its hydrolysis.

Original languageEnglish (US)
Pages (from-to)5739-5746
Number of pages8
JournalJournal of Organic Chemistry
Volume55
Issue number22
StatePublished - 1990

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sulfoxide
Stereochemistry
Hydrolysis
Disulfides
Deuterium
Conformations
Spectroscopic analysis
Boats
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Stereochemistry of the formation and hydrolysis of a dithioether dication. / Glass, Richard S; Broeker, Jeffrey L.; Firouzabadi, Habib.

In: Journal of Organic Chemistry, Vol. 55, No. 22, 1990, p. 5739-5746.

Research output: Contribution to journalArticle

Glass, RS, Broeker, JL & Firouzabadi, H 1990, 'Stereochemistry of the formation and hydrolysis of a dithioether dication', Journal of Organic Chemistry, vol. 55, no. 22, pp. 5739-5746.
Glass, Richard S ; Broeker, Jeffrey L. ; Firouzabadi, Habib. / Stereochemistry of the formation and hydrolysis of a dithioether dication. In: Journal of Organic Chemistry. 1990 ; Vol. 55, No. 22. pp. 5739-5746.
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abstract = "Naphtho[1,8-bc]-1,5-dithiocin 1-oxide (7) was prepared by oxidation of naphtho[1,8-6c]-1,5-dithiocin with sodium metaperiodate in aqueous methanol. The structure and conformation of sulfoxide 7 in the solid state was unequivocally established to be boat 7A with equatorial sulfoxide by X-ray crystallographic analysis. Sulfoxide 7 crystallizes in the triclinic space group P1 (no. 2) with a = 8.959 (2), b = 11.313(3), and c = 12.975 (3) {\AA}, α = 64.98 (2)°; β = 81.18 (2)°, γ = 78.67 (2)°, and Z = 4. The structure was solved by direct methods. Full-matrix least-squares refinement led to a conventional R factor of 0.040 after several cycles of anisotropic refinement. Dissolution of sulfoxide 7 in concentrated sulfuric acid produces disulfide dication 8, which on hydrolysis regenerates the sulfoxide. Deprotonation of sulfoxide 7 with methyllithium followed by treatment with D2O stereoselectively gives monodeuterated sulfoxide 7 (X = D). 1H NMR spectroscopic analysis of sulfoxide 7 (X = H) revealed that it is predominantly in chair conformation 7B with equatorial sulfoxide and the deuterium atom in the monodeuterated derivative is predominantly axial (7B, Ha = D). Disulfide dication 8 is deduced to be predominantly in boat conformation 8A by 1H NMR spectroscopic analysis and that derived from monodeuterated sulfoxide 7 has the deuterium predominantly axial (8A, Hb = D). Hydrolysis of the deuterated disulfide dication regenerates sulfoxide 7 with the deuterium axial. These surprising stereochemical results require retention of configuration at the sulfoxide sulfur both in the formation of disulfide dication 8 and its hydrolysis.",
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N2 - Naphtho[1,8-bc]-1,5-dithiocin 1-oxide (7) was prepared by oxidation of naphtho[1,8-6c]-1,5-dithiocin with sodium metaperiodate in aqueous methanol. The structure and conformation of sulfoxide 7 in the solid state was unequivocally established to be boat 7A with equatorial sulfoxide by X-ray crystallographic analysis. Sulfoxide 7 crystallizes in the triclinic space group P1 (no. 2) with a = 8.959 (2), b = 11.313(3), and c = 12.975 (3) Å, α = 64.98 (2)°; β = 81.18 (2)°, γ = 78.67 (2)°, and Z = 4. The structure was solved by direct methods. Full-matrix least-squares refinement led to a conventional R factor of 0.040 after several cycles of anisotropic refinement. Dissolution of sulfoxide 7 in concentrated sulfuric acid produces disulfide dication 8, which on hydrolysis regenerates the sulfoxide. Deprotonation of sulfoxide 7 with methyllithium followed by treatment with D2O stereoselectively gives monodeuterated sulfoxide 7 (X = D). 1H NMR spectroscopic analysis of sulfoxide 7 (X = H) revealed that it is predominantly in chair conformation 7B with equatorial sulfoxide and the deuterium atom in the monodeuterated derivative is predominantly axial (7B, Ha = D). Disulfide dication 8 is deduced to be predominantly in boat conformation 8A by 1H NMR spectroscopic analysis and that derived from monodeuterated sulfoxide 7 has the deuterium predominantly axial (8A, Hb = D). Hydrolysis of the deuterated disulfide dication regenerates sulfoxide 7 with the deuterium axial. These surprising stereochemical results require retention of configuration at the sulfoxide sulfur both in the formation of disulfide dication 8 and its hydrolysis.

AB - Naphtho[1,8-bc]-1,5-dithiocin 1-oxide (7) was prepared by oxidation of naphtho[1,8-6c]-1,5-dithiocin with sodium metaperiodate in aqueous methanol. The structure and conformation of sulfoxide 7 in the solid state was unequivocally established to be boat 7A with equatorial sulfoxide by X-ray crystallographic analysis. Sulfoxide 7 crystallizes in the triclinic space group P1 (no. 2) with a = 8.959 (2), b = 11.313(3), and c = 12.975 (3) Å, α = 64.98 (2)°; β = 81.18 (2)°, γ = 78.67 (2)°, and Z = 4. The structure was solved by direct methods. Full-matrix least-squares refinement led to a conventional R factor of 0.040 after several cycles of anisotropic refinement. Dissolution of sulfoxide 7 in concentrated sulfuric acid produces disulfide dication 8, which on hydrolysis regenerates the sulfoxide. Deprotonation of sulfoxide 7 with methyllithium followed by treatment with D2O stereoselectively gives monodeuterated sulfoxide 7 (X = D). 1H NMR spectroscopic analysis of sulfoxide 7 (X = H) revealed that it is predominantly in chair conformation 7B with equatorial sulfoxide and the deuterium atom in the monodeuterated derivative is predominantly axial (7B, Ha = D). Disulfide dication 8 is deduced to be predominantly in boat conformation 8A by 1H NMR spectroscopic analysis and that derived from monodeuterated sulfoxide 7 has the deuterium predominantly axial (8A, Hb = D). Hydrolysis of the deuterated disulfide dication regenerates sulfoxide 7 with the deuterium axial. These surprising stereochemical results require retention of configuration at the sulfoxide sulfur both in the formation of disulfide dication 8 and its hydrolysis.

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