Deoxyfluoroketohexoses: 4-deoxy-4-fluoro-D-sorbose and -tagatose and 5-deoxy-5-fluoro-L-sorbose

G. Venkat Rao, Lawrence Que, Laurance D. Hall, Thomas P Fondy

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

4-Deoxy-4-fluoro-α-D-sorbose (6) was prepared in crystalline form by the action of potassium hydrogen fluoride on 3,4-anhydro-1,2-O-isopropylidene-β-D-psicopyranose (3) followed by deacetonation. Under identical conditions 3,4-anhydro-1,2-O-isopropylidene-β-D-tagatopyranose (7) underwent epoxide migration to give 4,5-anhydro- 1,2-O-isopropylidene-β-D-fructopyranose (12), which after deacetonation yielded 4-deoxy-4-fluoro-D-tagatose (15) 5-deoxy-5-fluoro-α-L-sorbopyranose (16) the latter as the crystalline free sugar. The action of glycol-cleavage reagents on the isopropylidene acetals of the deoxyfluoro sugars was consistent with the assigned structures. The structures were established by 13C n.m.r. studies of the free deoxyfluoro sugars 6 and 16 of the isopropylidene acetal 13, and by 1H n.m.r. studies on the acetylated isopropylidene acetals 5 diacetate, 13 diacetate, and 14 diacetate. 5-Deoxy-5-fluoro-L-sorbose (16) was biologically active producing in mice effects characteristic of deoxyfluorotrioses and of fluoroacetate. 4-Deoxy-4-fluoro-D-tagatose (15) and 4-deoxy-4-fluoro-D-sorbose (6) produced no apparent effects in mice up to a dose of 500 mg/kg. The implications of these findings with respect to transport phosphorylation, and the action of aldolase on ketohexoses are discussed.

Original languageEnglish (US)
Pages (from-to)311-321
Number of pages11
JournalCarbohydrate Research
Volume40
Issue number2
DOIs
StatePublished - 1975

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Sorbose
Acetals
Sugars
Fluoroacetates
Crystalline materials
Fructose-Bisphosphate Aldolase
Phosphorylation
Glycols
Epoxy Compounds
tagatose
propylene
5-deoxy-5-fluoro-L-sorbose

ASJC Scopus subject areas

  • Biochemistry
  • Molecular Biology
  • Organic Chemistry

Cite this

Deoxyfluoroketohexoses : 4-deoxy-4-fluoro-D-sorbose and -tagatose and 5-deoxy-5-fluoro-L-sorbose. / Venkat Rao, G.; Que, Lawrence; Hall, Laurance D.; Fondy, Thomas P.

In: Carbohydrate Research, Vol. 40, No. 2, 1975, p. 311-321.

Research output: Contribution to journalArticle

Venkat Rao, G. ; Que, Lawrence ; Hall, Laurance D. ; Fondy, Thomas P. / Deoxyfluoroketohexoses : 4-deoxy-4-fluoro-D-sorbose and -tagatose and 5-deoxy-5-fluoro-L-sorbose. In: Carbohydrate Research. 1975 ; Vol. 40, No. 2. pp. 311-321.
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title = "Deoxyfluoroketohexoses: 4-deoxy-4-fluoro-D-sorbose and -tagatose and 5-deoxy-5-fluoro-L-sorbose",
abstract = "4-Deoxy-4-fluoro-α-D-sorbose (6) was prepared in crystalline form by the action of potassium hydrogen fluoride on 3,4-anhydro-1,2-O-isopropylidene-β-D-psicopyranose (3) followed by deacetonation. Under identical conditions 3,4-anhydro-1,2-O-isopropylidene-β-D-tagatopyranose (7) underwent epoxide migration to give 4,5-anhydro- 1,2-O-isopropylidene-β-D-fructopyranose (12), which after deacetonation yielded 4-deoxy-4-fluoro-D-tagatose (15) 5-deoxy-5-fluoro-α-L-sorbopyranose (16) the latter as the crystalline free sugar. The action of glycol-cleavage reagents on the isopropylidene acetals of the deoxyfluoro sugars was consistent with the assigned structures. The structures were established by 13C n.m.r. studies of the free deoxyfluoro sugars 6 and 16 of the isopropylidene acetal 13, and by 1H n.m.r. studies on the acetylated isopropylidene acetals 5 diacetate, 13 diacetate, and 14 diacetate. 5-Deoxy-5-fluoro-L-sorbose (16) was biologically active producing in mice effects characteristic of deoxyfluorotrioses and of fluoroacetate. 4-Deoxy-4-fluoro-D-tagatose (15) and 4-deoxy-4-fluoro-D-sorbose (6) produced no apparent effects in mice up to a dose of 500 mg/kg. The implications of these findings with respect to transport phosphorylation, and the action of aldolase on ketohexoses are discussed.",
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N2 - 4-Deoxy-4-fluoro-α-D-sorbose (6) was prepared in crystalline form by the action of potassium hydrogen fluoride on 3,4-anhydro-1,2-O-isopropylidene-β-D-psicopyranose (3) followed by deacetonation. Under identical conditions 3,4-anhydro-1,2-O-isopropylidene-β-D-tagatopyranose (7) underwent epoxide migration to give 4,5-anhydro- 1,2-O-isopropylidene-β-D-fructopyranose (12), which after deacetonation yielded 4-deoxy-4-fluoro-D-tagatose (15) 5-deoxy-5-fluoro-α-L-sorbopyranose (16) the latter as the crystalline free sugar. The action of glycol-cleavage reagents on the isopropylidene acetals of the deoxyfluoro sugars was consistent with the assigned structures. The structures were established by 13C n.m.r. studies of the free deoxyfluoro sugars 6 and 16 of the isopropylidene acetal 13, and by 1H n.m.r. studies on the acetylated isopropylidene acetals 5 diacetate, 13 diacetate, and 14 diacetate. 5-Deoxy-5-fluoro-L-sorbose (16) was biologically active producing in mice effects characteristic of deoxyfluorotrioses and of fluoroacetate. 4-Deoxy-4-fluoro-D-tagatose (15) and 4-deoxy-4-fluoro-D-sorbose (6) produced no apparent effects in mice up to a dose of 500 mg/kg. The implications of these findings with respect to transport phosphorylation, and the action of aldolase on ketohexoses are discussed.

AB - 4-Deoxy-4-fluoro-α-D-sorbose (6) was prepared in crystalline form by the action of potassium hydrogen fluoride on 3,4-anhydro-1,2-O-isopropylidene-β-D-psicopyranose (3) followed by deacetonation. Under identical conditions 3,4-anhydro-1,2-O-isopropylidene-β-D-tagatopyranose (7) underwent epoxide migration to give 4,5-anhydro- 1,2-O-isopropylidene-β-D-fructopyranose (12), which after deacetonation yielded 4-deoxy-4-fluoro-D-tagatose (15) 5-deoxy-5-fluoro-α-L-sorbopyranose (16) the latter as the crystalline free sugar. The action of glycol-cleavage reagents on the isopropylidene acetals of the deoxyfluoro sugars was consistent with the assigned structures. The structures were established by 13C n.m.r. studies of the free deoxyfluoro sugars 6 and 16 of the isopropylidene acetal 13, and by 1H n.m.r. studies on the acetylated isopropylidene acetals 5 diacetate, 13 diacetate, and 14 diacetate. 5-Deoxy-5-fluoro-L-sorbose (16) was biologically active producing in mice effects characteristic of deoxyfluorotrioses and of fluoroacetate. 4-Deoxy-4-fluoro-D-tagatose (15) and 4-deoxy-4-fluoro-D-sorbose (6) produced no apparent effects in mice up to a dose of 500 mg/kg. The implications of these findings with respect to transport phosphorylation, and the action of aldolase on ketohexoses are discussed.

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