The synthesis of diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride (original) (raw)
Related papers
Carbohydrate Research, 1983
Acetolysis of methyl 3-0-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-/l-Dglucopyranosyl)-2,4,6-tri-O-acetyl-cY-D-galactopyranoside afforded 3-0-(2acetamido-3,4,6-tri-O-acetyl-2-deoxy-~-D-glucopyranosyl)-1,2,4,6-tetra-O-acetyl-D-gak3CtOpyrZinOSC (2). Treatment of 2 in dichloromethane with hydrogen bromide in glacial acetic acid gave 3-O-(Zacetamido-3,4,6-tri-O-acetyl-2-deoxy-~-D-glucopyranosyl)-2,4,6-tri-O-acetyl-cy-D-galactopyranosyl bromide (3). The (Y contiguration of 3 was indicated by its high, positive, specific rotation, and supported by its 'H-n.m.r. spectrum. Reaction of 3 with Amberlyst A-26-p-nitrophenoxide resin in 1:4 dichloromethane-2-propanol furnishedp-nitrophenyl3-O-(2-acetamido-3,4,6tri-O-acetyl-2-deoxy-~-D-glucopyranosyl)-2,4,6-tri-O-acetyl-~-D-galactopyranoside (7). Compound 7 was also obtained by the condensation (catalyzed by silver trifluoromethanesulfonate-2,4,6-trimethylpyridine) of 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-/3-D-glucopyranosyl bromide with p-nitrophenyl 2,4,6-tri-O-acetyl-/3-D-galactopyranoside, followed by the usual deacylation-peracetylation procedure. 0-Deacetylation of 7 in methanolic sodium methoxide furnished the title disaccharide (8). The structure of 8 was established by 13C-n.m.r. spectroscopy.
Helvetica Chimica Acta, 1994
The triphenylstannyl p-u-glucopyranoside 4 was synthesized in one step from the 1.2-anhydro-a-uglucopyranose 3 with (hiphenylstannyl)lithium (Scheme 1). Transmetallation of 4 with excess BuLi, followed by quenching the dianion 7 with CD,OD gave (1s)-1 ,5-anhydro-3,4,6-triO -benzyl-f 1-2H]-u-glucitol (8) in 81% yield (Scheme 2). Trapping of 7 with benzaldehyde, isobutyraldehyde, or acroleine gave the expected p-Dconfigurated products 11,12, and 13 in good yields. Preparation of C-acyl glycosides from acid chlorides, such as acetyl or benzoyl chloride was not practicable, but addition of benzonitrile to 7 yielded 84% of the benzoylated product 14. Treatment of 7 with Me1 led to 15 (30%) along with 40% of 18, C-alkylation being accompanied by halogen-metal exchange. Prior addition of lithium 2-thienylcyanocuprate increased the yield of 15 to 50% and using dimethyl sulfate instead of Me1 led to 77% of 15. No a-u-anomers could be detected, except with ally1 bromide as the electrophile, which yielded in a 1:l mixture of the anomers 16 and 17. Introduction.-The occurrence as natural products, the biological activity, and the analogy to 0and N-glycosides have led to intense efforts for the synthesis of Cglycosides [ 1-81. Most of these syntheses are based on the reaction of nucleophiles with the electrophilic anomeric center, while syntheses based on an inversion of polarity of the anomeric center are relatively rare [l]. Anomeric monoanions are prone to rapid p elimination [9]. The first successful application of the inversion of polarity of the anomeric center was the chain elongation of doubly deprotonated, 2-hydroxy-1,3-dithianes, derivatives of aldehyde-saccharides [lo]. The first pyranosidic monoanion avoiding pelimination used the weakly reactive anions derived from 1-deoxy-1-nitroaldoses [ 1 1-14]. Reactive glycosyl monoanions usually lack functionality in the 2-position. Such carbanions, based on 2-deoxypyranosides, have been generated by reductive lithiation of 2-deoxy-~-g~ycopyranosyl chlorides [15], phenyl sulfides [ 161, or phenyl sulfones [ 171, by reductive samariation of phenyl sulfones [ 181, by deprotonation of glycals [19-221, and by transmetalation of 2-deoxy-~-glycopyranosylstannanes [23-261 or of the corresponding alkenylstannanes [23-261.
Carbohydrate Research, 1988
In a previous paper in this series2, we outlined our interest in the synthesis of some oligosaccharides containing ~-fume a-(1+3)-link4 to 2-acetamido&deoxy-~glucose. Our interest in this class of compounds was, to a large extent, motivated by a desire to obtain reference compounds in studies related to (1+3)-CAL-fucosyltransferase. This interest was, however, enhanced by recent reports associating a variety of such oligosaccharide suuctures with certain types of human ca11cers3-~.
Carbohydrate Research, 1989
The glycosphingolipids isolated from spermatozoa of a freshwater bivalve, Hyriopsis schlegelii, have a unique structure containing one or two mannosyl residues, novel linkages including an internal fucopyranosyl residue, as well as terminal xylosyl and 4-O-methyl-D-glucopyranosyluronic acid groups. The trisaccharide derivatives that constitute the partial structure of lipid IV were synthesized as follows. Condensation of 4,6-di-O-acetyl-2-azido-2-deoxy-3-0methyl-cY-D-galactopyranosyl bromide with 2-(trimethylsilyl)ethyl 4-O-acetyl-2-0benzyl-/3-L-fucopyranoside, in the presence of mercuric cyanide and mercuric bromide, gave the corresponding disaccharide in 87% yield. Condensation of methyl (2,3-di-O-acetyl-4-O-methyl-cuD -glucopyranosyl bromide)uronate with the appropriate OH-Cfree disaccharide derivative afforded the corresponding precursor of 4-O-Me-&D-GlcpA-(1~4)-[3-O-Me-aD -GalpNAc-(l~3)]-L-Fuc, namely 2-(trimethylsilyl)
Stereoselective synthesis of [13C]methyl 2-[15N]amino-2-deoxy-β-d-glucopyranoside derivatives
Carbohydrate Research, 2001
Efficient syntheses of three [ 13 C]methyl 2-[ 15 N]amino-2-deoxy-b-D-glucopyranoside derivatives are described. Amination of the D-glucal with (saltmen)Mn(15 N) proceeded with 11:1 stereoselectivity favoring the gluco configuration; subsequent methylation of the [ 15 N]lactol using [ 13 C]iodomethane and silver(I) oxide afforded the doubly labeled b glucoside in high yield. This compound served as the common precursor for three [ 13 C]methyl 2-[ 15 N]aminoglucosides: (2-[ 15 N]trifluoroacetyl-), (2-[ 15 N]acetyl-), and (2-[ 15 N]azido-). Selected heteronuclear coupling constants are reported.
Synthesis of some O-, S- and N-glycosides of hept-2-ulopyranosonamides
Carbohydrate Research, 2009
a b s t r a c t (O-Peracylated a-D-glucoand -galacto-hept-2-ulopyranosylbromide)onamides gave the corresponding (alkyl b-D-glyco-hept-2-ulopyranoside)onamides under Koenigs-Knorr conditions, and similar aryl glycosides were obtained with sodium phenolates; (aryl and hetaryl 2-thio-b-D-gluco-hept-2-ulopyranoside)onamides were formed with thiophenols in the presence of K 2 CO 3 in acetone, and reactions with aniline in CH 2 Cl 2 furnished (N-phenyl b-D-glyco-hept-2-ulopyranosylamine)onamides. Some deprotected derivatives of D-gluco configuration obtained by the Zemplén protocol showed no significant inhibition against rabbit muscle glycogen phosphorylase b.
Carbohydrate Research, 1983
A facile synthesis of p-nitrophenyl 2-acetamido-2-deoxy-4-O-P_D-galactopyranosyl-P-D-glucopyranoside was accomplished by saponification of the product obtained by reaction of 2-acetamido-3,6-di-O-acetyl-2-deoxy-4-0-(2,3,4,6-tetra-O-acetyl-/I-D-galactopyranosyl)-aD -glucopyranosyl chloride and Amberlyst A-26 p-nitrophenoxide. The reaction ofp-nitrophenyl2,3-O-isopropylidene-cc-D-mannopyranoside (7) with the easily accessible 2-methyl-[4,6-di-O-acetyl-2-deoxy-3-0-(2,3,4,6-tetra-Oacetyl-~-o-galactopyranosyl)-a-o-glucopyrano]-[2,1-d]-2-oxazoline proceeded readily, to give the protected trisaccharide derivative which, on deacetonation, followed by 0-deacetylation, produced one of the title trisaccharides, namely, p-nitrophenyl 6-0-(2-acetamido-2-deoxy-3-O-P-D-galactopyranosyl-~-D-glucopyranosyl)-a-~-mannopyranoside. Synthesis of the other trisaccharide, p-nitrophenyl 6-0-(2-acetamido-2-deoxy-4-0-/3-D-galactopyranosyl-~-D-glucopyranosyl)-c(-Dmannopyranoside was accomplished by a similar reaction-sequence when the corresponding 2-methyl-[3,6di-O-acetyl-2-deoxy-4-0-(2,3,4,6-tetra-O-acetyl-~-n-galactopyranosyl)-aD -glucopyrano]-[2,1-d]-2-oxazoline (19) reacted with 7. Preparation of oxazoline 19 was achieved via acetolysis of methyl 2-acetamido-2-deoxy-4-O-B-D-galactopyranosyl-~-Dglucopyranoside. The structures assigned to the final saccharides were supported by 'H-and i3C-n.m.r.-spectral data. *Synthetic Studies in Carbohydrates, Part XXIX. For Part XXVIII, see ref. 1. **To whom correspondence should be directed.
A novel glycosyl donor for synthesis of 2-acetamido-4-amino-2,4,6-trideoxy-a- d-galactopyranosides
Carbohyd Res, 2010
2-Azido-4-benzylamino-4-N-,3-O-carbonyl-2,4,6-trideoxy-D-galactopyranosyl trichloroacetimidate (14) was conveniently prepared in six steps by regioselective introduction of an N-benzyl carbamate at O-3 of 6-deoxy-D-glucal 6, followed by mesylation at O-4. Intramolecular displacement of the leaving group afforded oxazolidinone 11. Azidonitration of the bicyclic glycal 11 gave the glycosyl nitrate anomers 12 in good yield and stereoselectivity. Hydrolysis of the anomeric nitrates under aqueous conditions gave the pyranose 13, which was easily converted into the imidate 14. Glycosylation of cyclohexanol by 14 gave glycosides 16a and 16b in a ratio of 4:1.
[Synthesis of aminoethyl glycosides of the carbohydrate chains of glycolipids Gb3, Gb4 i Gb5]
Bioorganicheskaia khimiia
4-O-Glycosylation of 2-azidoethyl 2,3,6-tri-O-benzoyl-4-O-(2,3,6-tri-O-benzoyl-beta-D-galactopyranosyl)-beta- D-glucopyranoside with ethyl 2,3,4,6-tetra-O-benzyl- and ethyl 3-O-acetyl-2,4,6-tri-O-benzyl-1-thio-alpha-D-galactopyranoside in the presence of methyl trifluoromethanesulfonate led to trisaccharide 2-azidoethyl (2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl)-(1-->4)- (2,3,6-tri-O-benzoyl-beta-D-galactopyranosyl)-(1-->4)2,3,6-tri-O- benzoyl-beta-D-glucopyranoside and its 3"-O-acetylated analogue, 2-azidoethyl (3-O-acetyl-2,4,6-tri-O-benzyl- alpha-D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzoyl-beta-D- galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzoyl-beta-D-glucopyranoside, in yields of 85 and 83%, respectively. Deacetylation of the latter compound and subsequent glycosylation with 4-trichloroacetamidophenyl 3,4,6-tri-O-acetyl-2-deoxy-1-thio-2-trichloroacetamido-beta-D- galactopyranoside and 4-trichloroacetamidophenyl 4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetr...