6- Deoxy-6-fluoro-D-galactose

Unsaturated sugars, namely glycals, such as 3,4,6-tri-Oacetyl-l, 5-anhydro-2-dcoxy-D-r//v/-/w7o-hex-1-enetol and the d-/v.yo epimer react with xenon difluoride in the presence of a boron trifluoride-diethyl ether complex to give a mixture of C2 epimeric fluorides.45,46 Tri-O-acctyl-D-galactal treated with xenon difluoride in trichlorofluoromcthane below 5 C forms after hydrolysis (0.5 M HC1) 2-deoxy-2-fluoro-D-galactose in 63% overall yield.47... 

Synthesis of18F-labelled 2-deoxy-2-fluoro-D-galactose... 

Korytnyk and coworkers have shown that reactions of xenon difluoride with acetylated glycals in the presence of boron trifluoride are a convenient route for the synthesis of 1,2-difluoro sugars, while the addition of fluorine to the double bond occurred predominantly from the less hindered side and cis adducts were mainly formed75, 76. Stereoselective transformation of tri-O-acetyl-D-galactal with xenon difluoride at -20 to +5 °C, without a catalyst in CFC13, after hydrolysis, afforded 2-deoxy-2-fluoro-D-galactose in 63% yield77. 

J.N. Barlow, J.S. Blanchard, Enzymatic synthesis of UDP-(3-deoxy-3-fluoro)-D-galactose and UDP-(2-deoxy-2-fluoro)-D-galactose and substrate activity with UDP-galactopyranose mutase, Carbohydr. Res. 2000, 328, 473-480. 

The metabolic interconversion of 2-deoxy-2-fluoro-D glucose and 2-deoxy-2-fluoro-D-mannose (and their 6-phosphates) in tumour cells was investigated by F - NMR spectroscopy, and a mannose glucose equilibrium ratio of -4 1 was observed.The conversion of 2-deoxy-2-fluoro-D-galactose into its aluco-isomer via the action of a UDP-galactose epimerase has been observed in vivo in mice by use of F - NMR spectroscopy ... 

MHCl, refl. 30 min) gave 2-deoxy-2-fluoro-o-galactose (2DFGal, 86%). The crystal structure of l,3,4,6-tetra-0-acetyl-2-deoxy-2-fluoro-)9-D-galactopyr-anose has been reported. ... 

The reaction of gaseous [ F] fluorine or [ F] acetyl hypofluorite with tri-Q-acetyl-D-galactal has allowed the synthesis of 2-deoxy-2[ Flfluoro-D-galactose. Nucleophilic displacements employing [ F] fluoride ions on either methyl 3-Q-benzyl-4,6-0-benzylidene-2-Q-triflyl-p-D-mannopyranoside or 1,6-anhydro-3,4-di-Q-benzyl-2-Q-triflyl-p-D-mannopyranose have given access to 2-deoxy-2-[ F]fluoro-D-glucose. 

Related studies with 3-0-acetyl-l,2 5,6-di-0-isopropylidene-a-D-erythro-hex-3-enose (63, R = OAc), which can be prepared crystalline, and in good yield, from l,2 5,6-di-0-isopropylidene-a-D-rtbo-3-hex-ulose hydrate, have provided a useful new synthesis122 of D-gulose, because sodium borohydride causes efficient reduction to crystalline l,2 5,6-di-0-isopropylidene-a-D-guIose (64). Conversely, the unsaturated derivative (63, R = H) was produced, together with the 3-deoxy-3-fluoro-D-galactose compound on treatment of l,2 5,6-di-0-isopropyIidene-3-O-p-toIyIsulfonyl-D-gulose with tetrabutylammo-nium fluoride in acetonitrile.1223... 

Tri-0-acetyl-2-deoxy-2-fluoro-ce-D-glucopyranosylbromide, prepared from l,6-anhydro-4-0-benzyl-2-deoxy-2-fluoro-j3-D-glucose has been used in the synthesis of several 2-deoxy-2-fluoro- 3-D-glucopyranosides with phenol, 1,2 3.4-di-O-isopropylidene-D-galactose and 17-oxoestra-l,3,5(10)-trien-3-ol as agly-... 

Deoxy-2-[ F]fluoro-D-galactose can be prepared through an addition reaction to tri-O-acetyl-D-galactal (465), but better through Sn2 reaction (K F-Kryptofix 222 in MeCN) of methyl 3,4-0-isopropylidene-2-0-triflyl-6-0-trityl-y -D-talopyranoside (220 see Section 11,2), according to the cold synthesis. 

The A -bromo-, chloro-, and fluoro-acetyl derivatives of 2-amino-2-deoxy-D-glucose and -o-galactose have been prepared and tested for cytotoxic activity the per-O-acetylated A -bromoacetyl derivatives in either the glucose or galactose series were most effective against Friend erythroleukemia cells. A -nictotinoyl derivatives of 2-amino-2-deoxy-D-glucose and its ethyl a- and j8-pyranoside have been prepared. ... 

In the field of 2-aniino-2-deoxY-D-glucose disaccharides the sugar in various derivatised forms has been linked to D-galactose (/9-1,3-link)(and /9-1,6-link),D-glucose (iS-l,3-link), 2-amino-2-deoxy-D-glucose (j8-l,4-link) D-galacturonic acid fi-1,2-link)and L-iduronic acid (a-l,4-link).The 2-amino-2,4-dideoxy-4-fluoro compound (55) has been prepared by the oxazoline method and 2-amino-2-deoxy- -D-mannopyranosyl disaccharides have been produced from oximo-products obtained by use of a 2-deoxy-2-oximo-D-arabino-hexosyl bromide. A 4-amino-4-deoxy-D-rhamnosyl disaccharide (a-l,2-linked) has been made by way of 4-azido-corapounds. 

Deoxy-2-[ p]fluoro-D-galactose has been made by treating tri-O-acetyl-D-galactal with labelled acetyl hypofluorite followed... 

Thus, 2-fluoro-2-deoxy-, 3-fluoro-3-deoxy-, 4-fluoro-4-deoxy-, and 5-fluoro-5 deoxy pyranoses can be prepared by treating the corresponding triflate with TASF. 4-Fluoro-4-deoxy-D-galactoses have also been prepared by reacting the free hydroxyl... 

Figure 4. F NMR spectra of (A) two-dimensional NOESY exchange of 3 mM 4-fluoro-4-deoxy-galactose and 2 mM receptor at 25°C. Diagonal peaks show the one-dimensional spectrum which is projected on the top of the map. (B) 1.6 mM 4-fluoro-4-deoxy glucose and 0.8 mM receptor at 25°C and (C) 2°C. (D) 1 mM 4-fluoro-4-deoxy-galactose and 2 mM receptor at 2° C.

---