Di-O-isopropylidene-p-D-fructopyranose

A 3-0-benzylated D-fructose derivative was produced from l,2 4,5-di-O-isopropylidene-P-D-fructopyranose under standard conditions (Scheme 26). Transient 3-0-benzylated D-fructose resulting from acidic hydrolysis was reacted with thiocyanic acid without intermediate purification. This sequence afforded a mixture of isomeric spiro-OZT on pyran and furan templates, which was difficult to separate, even if standard acetylation was applied. 

Scheme 8 Stereoselective synthesis of di-P-D-fructopyranose 1,2 2,1 dianhydride (14) from 2,3 4,5-di-O-isopropylidene-P-D-fructopyranose by HF activation...

Chloro-1 -deoxy-2,3 4,5-di- O -isopropylidene- p-D-fructopyranose, C-79 l-Chloro-l-deoxy-2,3 4,6-di-0-isopropylidene-a-L-sorbofuranose, C-101 1-Chloro-l-deoxyfructose i>-form, C-79 l-Chloro-l-deoxy-2,3-0-isopropylidene-p-D-fructofuranose, C-79 1-Chloro-1 -deoxy-2,3-0 -isopropylidene-a-L-sorbofuranose, C-101... 

Wittig reactions were used to convert 2,3 4,5-di-O-isopropylidene-p-D-fructopyranose into the separable isomers (72), one of which could be converted to (-)-talaromycin A (sugar carbons indicated). Acid treatment of (73) gives talaromycin B, the epimer at C-5 (fructose numbering), with C-6 of the sugar now endocyclic. ... 

D-Glucose (p-bromophenyl)-hydrazone132 D-Mannose (p-bromo-phenyl) hy drazone133 1,2 4,5-Di-O-isopropylidene-/3-D-fructopyranose134 2,3 4,5-Di-O-isopropylidene-/3-D-fructopyranose R-Cellobiose103 135 137 Sucrose-sodium bromide, dihydrate138... 

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... 

Deoxy-am fno-hexopyranosyl fluoride a-G-forrrv, 3,6-Dibenzoyl, D-196 2-Deoxy-/> xo-hexopyranosyl fluoride a-G-form 3,6-Dibenzoyl, D-197 2-Deoxy-/j x< -hexopyranosyl fluoride a-D-/orm 4,6-Dibenzoyl, D-197 2-Deoxy-n7)o-hexopyranosyl fluoride (x-G-fomv, 3,6-Dibenzoyl, D-198 2-Deoxy-am )ino-hexopyranosyl fluoride a-D-/< rm Tri-Ac, D-196 2-Deoxy-am6ino-hexopyranosyl fluoride a-D-/< rm Tribenzoyl, D-196 2-Deoxy-/vxo-hexopyranosyl fluoride a-D-/owi Tribenzoyl, D-197 2-Deoxy-W6o-hexopyranosyl fluoride a.-G-fomv, Tribenzoyl, D-198 2-Deoxy-ara >ino-hexopyranosyl fluoride a.-G-form, D-196 2-Deoxy-/> xo-hexopyranosyl fluoride a.-G-form, D-197 2-Deoxy-W6o-hexopyranosyl fluoride a-G-form, D-198 l-Deoxy-l-iodo-2,3 4,5-di-0-isopropylidene-p-D-fructopyranose, D-254 l-Deoxy-l-iodo-2,3 4,6-di-0-isopropylidene-a-L-sorbofuranose, D-273... 

Primary alcohol groups in several protected ribo-, fructo- and glucofuranoses including 2,3,4-tri-O-benzoyl-D-glucose, 1,2-isopropylidene-D-xylo-furanose, 2,3 4,5-di-0-isopropylid-ene-D-fructopyranose, methyl 2,3-O-isopropylidene-P-D-ribofuranoside, l,2-0-isopropylidene-3,5-0-benzylidene-D-glucofuranose and... 

Synthesis from o-fructose Syntheses of 7a-cp/-hyacinthacine A2 (7-deoxya-lexine, 139) and 5,7a-di-e/7/-hyacinthacine A3 (143) from D-fmctose have been reported (Scheme 10). Mesylation of 3-(9-benzoyl-4-(9-benzyl-l,2-0-isopropylidene-p-D-fructopyranose (128) followed by azidolysis gave 5-azido-3-(9-benzoyl-4-0-benzyl-... 

Benzoyl, 4,5-di-Ac 4,5-Di-0-acetyl-3-0-benzoyl-l,2-0-isopropylidene-p-D-fructopyranose C20H24O9 408.404 Mp 77-78°. [a]o -132.5 (EtOH). 

Ditosyl, 3-benzoyl 3-O-Benzoyl-l,2-0-isopropylidene-4,5-di-0-tosyl-P-D-fructopyranose... 

Di-0-benzylidene-p-D-fnictopyranose, F-84 2,3 4,5-Di-0-benzylidene-l-0-methyl-p-D-fructopyranose, F-84 2,3 4,5-Di-0-benzylidene-l-0-tosyl-p-D-fructopyranose, F-84 l,2 4,5-Di-0-cyclohexylidene-p-D-fnictopyranose, F-84 l,2 4,5-Di-0-isopropylidenefructopyranose D-form 3-O-Benzyl, D-714 l,2 4,5-Di-0-isopropylidenefructopyranose D-form, D-714 l,2 4,5-Di-0-isopropylidenefructopyranose D-form, D-714 2,3 4,5-Di-0-isopropylidenefructopyranose D-form, D-715 2,3 4,5-Di-0-isopropylidenefructopyranose D-form, D-715 3,4 5,6-Di-0-isopropylidene-D-ara6BM7-hex-2-uIosonic acid, H-111 l,2 4,5-Di-0-isopropylidene-3-0-mesyl-P-D-fructopyranose, D-714 l,2 4,5-Di-0-isopropylidene-3-C-methyl-p-D-fructopyranose, M-248 2,3 4,5-Di-0-isopropylidene-l-0-methyl-P-D-fructopyranose, D-715 2,3 4,5-Di-0-methylenefructopyrauose -D-form, D-729... 

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-... 

Conformational analyses by n.m.r. and computational methods have been reported for the following compounds l,2-anhydro-3,4,6-tri-0-benzyl-P-D-talopyranose, anhydro sugars 13 and similar hexopyranose derivatives, methyl 3,4-0-isopropylidene-a- and P-D-galactopyranoside and their di-O-acetates and di-O-methyl ethers, 3,4-0-(/ )-benzylidene-D-ribono-1,5-lactone (see Chapter 6), and 6-deoxy-6-phosphonoyl-D-fructopyranoses (see Chapter 17 for synthesis). D-Glucospyranosylamine, its tetra-O-acetate and 4,6-0-benzylidene acetal and several N-acylated derivatives, together with D-[l- C]glucopyranosylamine, have been used in a conformational study by n.m.r. spectroscopy aimed at probing the existence of the reverse anomeric effect. ... 

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