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Deoxyfluorination of alcohols was carried out using N,N-diethyl-alpha, alpha-difluoro-(m-methylbenzyl)amine (DFMBA). Primary alcohols were effectively converted to fluorides under microwave irradiation or conventional heating. Deoxyfluorination of an anomeric hydroxy group in sugars by DFMBA proceeded at below room temperature and glycosyl fluorides could be obtained in good yields. The deoxyfluorination reaction chemoselectively proceeded and various protecting groups on the sugar can survive under the reaction conditions.

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Selective deprotection of photolabile anomeric 2-nitrobenzyl acetals was achieved using continuous flow photo-reactor (UV radiation at 355 nm) in methanol-water. Various protecting groups such as acetyl, benzyl, benzoyl, benzylidine, TBS, etc. were found to be highly stable during the photolysis.

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Tetrahydropyran – Wikipedia,
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Standard chemical methods involving the use of O-acetylated glycosyl trichloroacetimidates as glycosylating agents were used to prepare the five 1,3-dideoxynojirimycin-3-yl beta-(1?3)-linked oligo-glucosides (1-5) and also the beta-(1?6)-bonded glucobiose (gentiobiose)-based analogue 6 as potential fungicides. In the course of the work, the beta-(1?6), beta-(1?6)-linked analogue 8 of 6 and 6-O- and 4-O-beta-glucopyranosyl-deoxynojirimycins 7 and 9, respectively, were also produced.

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Methyl (2E,4E?)-5-(2?,3?,4?,6?-tetra-O-acetyl-p-D- glucopyranosyloxy)penta-2,4-dienoate 16a, assembled by a Wittig condensation of tributyl(methoxycarbonylmethylene)phosphorane 19a and (2E)-3-(2?,3?,4?,6?-tetra-O-acetyl-?- Dglucopyranosyloxy)propenal 20, displays excellent Re-face reactivity towards diethyl azodicarboxylate 15a, bis(2,2,2trichloroethyl) azodicarboxylate 15b, dibenzyl azodicarboxylate 15c, diisopropyl azodicarboxylate 15d and di-tertbutyl azodicarboxylate 15e in thermal hetero-Diels-Alder reactions to give the cycloadducts 17a-e. When subjected to the action of hydrogen over palladium-carbon, the cycloadducts 17a, 17b, 17d and 17e undergo hydrogenation of their olefinic bonds to give the dihydro derivatives 18a, 18b, 18d and 18e; in the case of the cycloadduct 17c, hydrogenolysis of the benzyloxycarbonyl group also occurs to give methyl (35)-2,3,4,5-tetrahydropyridazine-3carboxylate Ib with an ee of 98% and 2,3,4,6-tetra-O-acetyl-?-D-glucopyranose 22. Compound Ib, with an ee of 98%, is also available from the dihydro derivative 18e by the action of trifluoroacetic acid; however, under the acidic conditions, a condensation reaction between the aglycone Ib and the glycone 22 competes to give methyl (35)-2,3,4,5tetrahydro-2-(2?,3?,4?,6?-tetra-0-acetyl- ?-D-glucopyranosyl)pyridazine-3-carboxylate25. Sodium (35)-2,3,4,5-tetrahydropyridazine-3-carboxylate le, with an ee of 99%, is available from the ester Ib by a saponification reaction. The trifluoroacetic acid salt 27, with an ee of 95%, is obtained from benzyl (35,6S)1,2-bis(tert-butoxycarbonyl)-1,2,3,6-tetrahydro-6-(2?,3?, 4?,6?-tetra-O-acetyl-beta-D-glucopyranosyIoxy)pyridazine-3- carboxylate 17g by a hydrogenation-trifluoroacetolysis sequence. A hetero-Diels-Alder reaction involving the benzyl pentadienoate 16c and di-tert-butyl azodicarboxylate 15e provides the cycloadduct 17g. The Royal Society of Chemistry 1999.

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The recently isolated natural product harounoside, namely 5,10-dihydroxy-2H-naphtho[2,3-c]pyran-beta-D-bisglucopyranoside, was conveniently synthesized for the first time from pentalongin in 84% yield over three steps. Georg Thieme Verlag Stuttgart.

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Reaction of (-) 2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylic acid with per-O-acetyl-D- and L-glucopyranosyl bromides yielded diastereomeric per-O-acetylated glycopyranosyl 2-tert-butyl-2-methyl-1,3-benzodiazole-4-carboxylates. Their 1H-n.m.r. signals, especially the strong singlet peaks of tert-Bu and Me groups in the 1-ester portion were diagnostic for the determination of the D,L-configuration and optical purity of monosaccharides. Reaction of (-)2-tert-butyl-2-methyl-1,3-benzodioxole-4-carboxylic acid with per-O-acetyl-D-and L-glucopyranosyl bromides yielded diastereomeric per-O-acetylated glycopyranosyl 2-tert-butyl-2-methyl-1, 3-benzodiazole-4-carboxylates. Their H-n.m.r. signals, especially the strong singlet peaks of tert-bu and Me groups in the 1-ester portion were diagnostic for the determination of the D,L-configuration and optical purity of monosaccharides.

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There is provided a process for the selective anomeric deacetylation of sugar derivatives, which may be substituted by substituents such as acetoxy, chloracetoxy, alkoxy, azido, etc., by means of tin compounds R3 SnOR’ or R2 SnO where R is lower alkyl resulting either directly in the desired anomeric compound or in an intermediate which is converted to the desired compound by silica or by acid hydrolysis.

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A novel and high yielding glycosylation protocol with glycosyl ortho-alkynylbenzoates as donors and iodine as promoter is described. The donors are stable and can be chemoselectively activated in the presence of thioethyl and thiophenyl glycosides. The application of this methodology in one-pot consecutive glycosylation reaction is described.

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The ammonia desorption chemical ionization (HN3-DCI) mass spectra of peracetylated gentiobiose (1) and two isotopically labelled gentiobioses (2 and 3) were examined.Compound 2 is labelled with trideuteroacetyl groups in the non-reducing moiety and 3 with trideuteroacetyl groups in the reducing moiety.It is shown that the + ion is not found direct from + by loss of ketene but appears to be formed by way of a nucleophilic acyl substitution reaction resulting in a neutral species which complexes with NH4+.The disaccharides undergo cleavage at either side of the glycoside oxygen joining the two sugar residues, a process which is accompanied by addition of H or CH3CO to afford neutral species which complex with NH4+.The structure of the ions resulting from H transfer have been inferred by comparison of their mass-analysed ion kinetic energy (MIKE) spectra with MIKE spectra of the + ions compounds of established structure.A ring fragmentation reaction of 1, 2 and 3 is reported.

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Tetrahydropyran – Wikipedia,
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A simple and mild method for regioselective anomeric deacetylation of peracetylated glycopyranoses using copper(II) acetate dihydrate and methanol/water (9:1) is described.

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Tetrahydropyran – Wikipedia,
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