4-Deoxy-4-fluoro-D-fructose

Deoxy-4-fluoro-D-fructose (552) was prepared (59%) by fermentation of 3-deoxy-3-fluoro-D-mannitol with Gluconobacter oxydans. The structure of 552 (fi-T) form) was confirmed by the n.m.r. spectrum, which resembles that of 4-deoxy-4-fluoro-Q -D-sorbopyranose (553) 552 was identical with one of the products obtained from the oxirane-ring opening of 3,4-anhy-dro-l,2-0-isopropylidene- -D-tagatopyranose with KHFj. 

Deoxy-4-fluoro-D-glucose 4-deoxy-4-fluoro-D-fructose 1,6-bisphophate 1 30 HK11 5000 PCI" FK" 2000 71... 

The Specificity of Pyranose-2-oxidase and the of 4-Deoxy-4-fluoro-D-fluoro-D-fructose... 

We have developed preparative enzymatic syntheses of several unusual hexoketoses using fructose-1,6-diphosphate aldolase (FDP-aldolase, E.C.4.1.2.13) as catalyst and dihydroxyacetone phosphate (DHAP) and an aldehyde as substrates (15). The enzyme appears to be very specific for DHAP but will accept a variety of aldehydes as acceptors. The ketose-1-phosphates prepared are converted to the phosphate free ketoses after removal of the phosphate group by acid- or phosphatase-catalyzed hydrolysis. The ketoses can be isomerized stereospecifically to aldoses catalyzed by glucose isomerase (E.C.5.3.1.5.) from Flavobacteriuum arborescens. The equilibrium mixtures of aldoses and ketoses are then separated by chromatography on Dowex 50 (Ba ) or Dowex 1 (HSO "). Figure 1 illustrates the preparation of a mixture of 6-deoxy-6-fluoro-D-fructose... 

O -Benzoyl-1,2-0 -isopropylidene- p-D-fructopyranose, 1-62 1-0-Benzyl-3-deoxy-3-fluoro-D-fructose, D-74 l-Bromo-l-deoxy-2,3 4,5-di-0-isopropylidene-p-D-fructopyranose, B-67 Butyl p-D-fructofuranoside, F-84... 

A number of studies on the metabolism of 3FG and 4FG in Locusta miaratoria have been undertaken. Both 3FG and 4FG are toxic to locust with LD50 s of 4.8 mg/g and 0.6 mg/g respectively. In vitro studies showed that 3FG is metabolized in the fat body, via the NADP-linked aldose reductase, to 3-deoxy-3-fluoro-D-glucitol (3FGL). This metabolite was detected in the hemolymph of the insect and shown to be both a competitive inhibitor and a substrate for NAD-linked sorbitol dehydrogenase, thereby generating 3-deoxy-3-fluoro-D-fructose (3FF) (541. Subsequently, it was shown by in vivo radio-respirometric analysis of C02 and appropriate chase experiments, that 3FG metabolism irreversibly inhibits glycolysis and not the hexose monophosphate shunt or tricarboxylic acid cycle (55). In addition, the release of fluoride ion and H20 from D-[3- H]-3FG was also observed. Based on the mechanism of aldolase (55) and triosephosphate isomerase... 

Enzymatic dehydrogenation of 3-deoxy-3-fluoro-D-mannitol using enzymes of Gluconobacter oxydana provides a route to i4,-deox -4.-fluoro-D-fructose, whose structure was confirmed b H, C, and F n.m.r. spectroscopy. The molecule adopts the C (D) conformation in aqueous solution. 

Several fluoro analogs of ketoses have been reported 1,6-dideoxy-1,6-difluoro-D-fructose was readily obtained from 2,3-O-isopropyli-dene-l,6-di-0-p-tolylsulfonyl-)3-D-fructofuranose by treatment with potassium fluoride in 1,2-ethanediol under a stream of carbon dioxide.96 Surprisingly, although the 6-sulfonyloxy group would be expected to be more reactive than the 1-sulfonyloxy group,97-99 no selectivity was observed. The failure to obtain 1-deoxy-l-fluoro-D-fructopyranose96 from 2,3 4,5-di-0-isopropylidene-l-0-(methylsulfonyl) (or p-nitro-phenylsulfonyl)-/3-D-fructopyranose or phenyl 3,4,5-tri-O-acetyl-l-O-(methylsulfonyl)-/3-D-fructopyranoside by treatment with potassium or sodium fluoride in 1,2-ethanediol, N,N-dimethylformamide, or form-amide at elevated temperatures may be attributed to the fact that nu-... 

Stoichiometric quantities of uridine diphosphate glucose were used, in the presence of a transfer enzyme, sucrose synthetase, in the soluble state (extraction given). Coupling with modified D-fructose gave sucroses modified on the D-fructosyl group, on the 1 -3-mmol scale. Thus were prepared l -deoxy-l -fluoro- (59%),98 4 -deoxy-4 -fluoro- (16%), and l -azido-l -deoxy-sucrose (15%).71 6-Deoxy-6-fluoro-D-glucose was isomerized to 6-deoxy-6-fluoro-D-fructose with isomerase, and gave 6 -deoxy-6 -fluoro-sucrose.71... 

The chemical synthesis of deoxyfluoro-D-fructoses has been restricted to 1-deoxy-l-fluoro-D-fructose ( 3) and 1,6-dideoxy-l,6-difluoro-D-fructose ( 4). The... 

Deoxy-3,5-di-0-toluoyl-p-D- r> /Aro-pentofuranosyl chloride, D-357 l-Deoxy-l-fluoro-2,3 4,5-di-0-isopropylidene-D-fructose, D-73... 

Benzyl 3-bromo-3-deoxy-2-0-methyl-p-D-xylopyranoside, B-103 Benzyl 3-bromo-3-deoxy-4-0-methyl-p-D-xylopyranoside, B-103 Benzyl 3-deoxy-3-fluoro-p-D-glucopyranoside, D-89 Benzyl 3-deoxy-3-iodo-p-L-xylopyranoside, D-280 Benzyl 2,4-di-D-benzoyl-3-bromo-3-deoxy-a-D-xylopyranoside, B-103 Benzyl 2,4,6-tri-D-acetyl-3-deoxy-3-fluoro-p-D-glucopyranoside, D-89 1 - O -Benzyl-3-deoxy-3-fluoro-D-fructose, D-74 3-Bromo-3-deoxy-l,2 5,6-di-0-isopropylidene-a-D-allofuranose, B-56 3-Bromo-3-deoxyglucose D-form, B-75 3-Bromo-3-deoxymannose D-form, B-88 3 -Bromo-3 -deoxythymidine 5 -Trityl, B-99 3 -Bromo-3 -deoxythymidine, B-99... 

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