A new route to 3-deoxy-3-fluoro-D-glucose

Chemistry of apiose. VI. Influence of reaction conditions and stereochemistry on some thioacetate displacemtnes with carbohydrate sulfonates

“…29 An alternative route to 3-thioglucose derivatives is by the reaction of sulfur nucleophiles on the readily available 1,2:5,6di -Oispropylidene-3 -O-p-tolylsulfonyladallofuranose. 30 Treatment of this sulfonate with 3 equiv of potassium thioacetate in DMF at 100°for 2 days gave a 70% yield (81% based on unrecovered sulfonate) of 3-S-acetyl-l,2:5,6-di-O-isopropy lidene-3 -thio-a-D-glucofuranose, a syrup previously prepared by acetylation of 1,2:5,6 -di -O-isopropylidene-3-thio--D-glucofuranose. 29 The formation of a small amount (<3%) of 3-O-acetyl-1,2:5,6-di-0 -isopropylideneadglucofuranose was attributed to the presence of approximately 10% acetate ion in the potassium thioacetate used (determined by integration of the nmr spectrum).…”

3-Fluoroazetidinecarboxylic Acids and trans,trans-3,4-Difluoroproline as Peptide Scaffolds: Inhibition of Pancreatic Cancer Cell Growth by a Fluoroazetidine Iminosugar

“…The combined organics were dried (MgSO 4 ), filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography (cyclohexane/ethyl acetate, 6:1 → 4:1) to give the title compound 21 as clear oil (4.70 g, 89%): HRMS (ESI +ve) found 285.1110 [M + Na] + , C 12 H 19 FNaO 5 + requires 285.1109; [α] D 20 −19.7 ( c 1.06, CHCl 3 ) [lit . [α] D 20 −37.0 ( c 1.00, CHCl 3 )]; ν max (thin film) fingerprint region only; δ H (CDCl 3 , 400 MHz) 1.32 (3H, s, CH 3 ), 1.36 (3H, s, CH 3 ), 1.44 (3H, s, CH 3 ), 1.50 (3H, s, CH 3 ), 4.03 (1H, dd, H6, J 6,5 4.8, J gem 8.8), 4.10 (1H, ddd, H4, J 4,3 2.2, J 4,5 8.3, J 4,F 29.1), 4.12 (1H, dd, H6′, J 6′,5 6.1, J gem 8.8), 4.28 (1H, ddd, H5, J 5,6 4.9, J 5,6′ 6.1, J 5,4 8.3), 4.69 (1H, dd, H2, J 2,1 3.8, J 2,F 10.6), 5.01 (1H, dd, H3, J 4,3 2.2, J 3,F 49.9), 5.95 (1H, d, H1, J 1,2 3.7); δ C (CDCl 3 , 100 MHz) 25.1 (CH 3 ), 26.2 (CH 3 ), 26.7 (CH 3 ), 27.0 (CH 3 ), 67.2 (C6), 72.0 (d, C5, J 5,F 7.0), 80.6 (d, C4, J 4,F 19.1), 82.5 (d, C2, J 2,F 33.4), 93.8 (d, C3, J 3,F 184.4), 105.2 (C1), 109.5 ( C (CH 3 ) 2 ), 112.4 ( C (CH 3 ) 2 ); δ F (CDCl 3 , 376 MHz) −207.6 (ddd, J F,2 10.8, J F,4 29.2, J F,3 49.8); m / z (ESI +ve) 263 ([M + H] + , 100), 285 ([M + Na] + , 72).…”

Short Communications

“…Biochemical studies already reported with 2-deoxy-2-fluoroerythritol (Smith, Anderson, Keppie, Kent & Timmis, 1965), which acts as a growth inhibitor of Brucella abortus, and 2-deoxy-2-fluoroglycerol (O'Brien & Peters, 1958) support this suggestion. It is only recently, however, that fluoropentoses (Wright & Taylor, 1967) and fluorohexoses (Buck, Foster, Hems & Weber, 1966) with fluorine in other than the anomeric (reviewed by Michael & Klemer, 1961) or terminal positions (Taylor & Kent, 1958) of monosaccharides have become available.We now report some preliminary biochemical results with 3FG* (Buck et al 1966). The structure of this compound has been established (Foster, Hems & Weber, 1967) by degradation to the known 3-deoxy-3-fluoro-D-xylose (Wright & Taylor, 1967).Materials and methods.…”