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 journalArticlepeer-review

17 Scopus citations

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 - Apr 1975

Bibliographical note

Funding Information:
*For a preliminary report, see ref. 1. **Present address: Endo Laboratories, Garden City, New York 11530, U. S. A. TDepartment of Chemistry, Massachusetts Institute oFTechnology, Cambridge, Massachusetts 02139, U. S. A. PDepartment of Chemistry, University of British Columbia, Vancouver 8, Canada. itRecipient of Research Career Development Award No. 70332 from the National Cancer Institute.

Funding Information:
use in confirming the 13C n.m.r. assignments. This work was supported by Grant CA-10250 from the National Cancer’ Institute.

Fingerprint Dive into the research topics of 'Deoxyfluoroketohexoses: 4-deoxy-4-fluoro-D-sorbose and -tagatose and 5-deoxy-5-fluoro-L-sorbose'. Together they form a unique fingerprint.

Cite this