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1.
Abstract We have prepared three series of functionalized disaccharides of the type A(6→n)B and a trisaccharide with the formula A- O-B- O-C, in which A = D-glucose (or its derivatives) and both B and C are any of D-fructose, D-galactose, D-glucose, xylitol and glycerol (or their derivatives). These compounds resulted from the regiospecific functionalization of either A or B and either the partial or total deprotection of either 6- O-(3-deoxy-1,2:5,6-di- O-isopropylidene-α-D-glucofuranos-3-yl)-3- O-alkyl-1,2- O-isopropylidene-α-D-glucofuranose or its analogues of type 1 described in part I. 1 We also report results on surface activity and biological properties of some of the molecules prepared. 相似文献
2.
Abstract Starting from L-fucose, D-glucose and lactose, methyl O-[2,3-di- O-benzoyl- 4, 6- O-(4-methoxybenzylidene)-β-D-glucopyranosyl]-(1→4)-2,3-di- O-benzoyl-α-L-fucopyranoside and methyl O-(2,3,4,6-tetra- O-benzyl-β-D-galactopyranosyl)-(1→4)- O-(2,3,6-tri- O-benzyl-α-D-glucopyranosyl)-(1→4)- O-(methyl 2,3-di- O-benzoyl-β-D-glucopyranosyluronate)-(1→4)-2,3-di- O-benzoyl-α-L-fucopyranoside were synthesized. Removal of protecting groups gave the tetrasaccharide repeating unit of the antigen from Klebsiella type-16 in the form of its methyl ester methyl glycoside. 相似文献
3.
Cellulose, which comprises D-glucose and L-glucose (D,L-cellulose), was synthesized from D-glucose (1D) and L-glucose (1L) via cationic ring-opening polymerization. Specifically, the ring-opening copolymerization of 3-O-benzyl-2,6-di-O-pivaloyl-β-D-glucopyranoside (2D) and 3-O-benzyl-2,6-di-O-pivaloyl-β-D-glucopyranoside (2L), synthesized from compounds 1D and 1L, respectively, in a 1:1 ratio, afforded 3-O-benzyl-2,6-di-O-β-D,L-glucopyranan (3DL) with a degree of polymerization (DPn) of 28.5 (Mw/Mn?=?1.90) in quantitative yield. The deprotection of compound 3DL and subsequent acetylation proceeded smoothly to afford acetylated compound 4DL with a DPn of 18.6 (Mw/Mn?=?2.08). The specific rotation of acetylated compound 4DL was?+?0.01°, suggesting that acetylated compound 4DL was optically inactive cellulose triacetate. Furthermore, before acetylation, compound 4DL was an optically inactive cellulose comprising an almost racemic mixture of D-glucose and L-glucose. Compound 4DL was an amorphous polymer. This is the first reported synthesis of optically inactive D,L-cellulose. 相似文献
4.
Synthesis of three new stable spirodifuranose derivatives ( 3, 5, and 7), which cannot be obtained easily using ordinary synthetic methods, has been achieved by reduction of 3- O-acetyl and 3- O-methyl derivatives of (4 R)-1,2- O-alkylidene-5-eno-4,7-epidioxy-5,6,8-trideoxy- α-D- threo-1,4-furano-4,7-diulo-octoses ( 1, 4, and 6). 相似文献
5.
Abstract C-6 ring opening of 5,6-cyclic sulfate derivatives of protected manno and glucofuranose with carbohydrate alkoxides gave ether linked pseudo-di or trisaccharides. Use of methyl 2,3- O-isopropylidene-5,6- O-sulfuryl-α-D-mannofuranoside 1 led to protected pseudo-disaccharide D-Glc f-(3→6)-D-Man f-(5→6)-D-Man f 4 and protected pseudo-trisaccharide D-Man f-(6→3)-D-Glc f-(6→3)-D-Glc f 11 derivatives in 66% and 41% overall yields, respectively. 相似文献
6.
ABSTRACT Ammonium 2,3,6-trideoxy-2,6-epithio-D- manno-2-octenoate ( 8), ammonium 2,3,6-trideoxy-2,6-epithio-D- glycero-D- talo-octanoate ( 10a), ammonium 2,3,6-trideoxy-2,6-epithio-D- glycero-D- galacto-octanoate ( 10b) and ammonium 2,3,6-trideoxy-2,6-epithio-oxa-D- glycero-D- galacto-octanoate (13) have been synthesised as potential inhibitors of the enzyme CMP-KDO synthetase. The key step in the synthesis of 8 was the elimination of water from methyl 3,6-dideoxy-4,5:7,8-di- O-isopropylidene-6-thio-D- manno-2-octulosonate ( 4) using chlorodiphenylphosphine, imidazole and bromine to give the unsaturated methyl 2,3,6-trideoxy-2,6-epithio-4,5:7,8-di- O-isopropylidene-D- manno-2-octenoate ( 5). For the synthesis of 10a and 10b, zinc reduction of methyl 3,6-dideoxy-4,5:7,8-di- O-isopropylidene-6- S-(4-methoxybenzyl)-6-thio-2- O-(trichloro- tert-butoxycarbonyl)-D- manno-2-octenoate ( 2) gave an epimeric mixture of an α-hydroxyester 6 which was ring closed by in situ activation of the hydroxyl group using triphenylphosphine and tri-iodoimidazole followed by cleavage of the p-methoxybenzyl group to give 7a and 7b, which then were deprotected to give 10a and 10b. 相似文献
7.
Abstract We have determined the preferred conformers in solution by a detailed NMR analysis using COSY and HETCOR experiments of three inositol isomers: myo ( 1), scyllo ( 2) and epi ( 3) plus sixteen derivatives of myo-inositol: 1,2,3,4,5,6-hexa- O-acetyl- myo-inositol ( 4), 1,2,- O-isopropylidene- myo-inositol ( 5), 1,2:4,5-di- O-isopropylidene- myo-inositol ( 6), 3,4,5,6-tetra- O-acetyl-1,2- O-isopropylidene- myo-inositol ( 7), 3,4,5,6-tetra- O-acetyl- myo-inositol ( 8), 1,2- O-isopropylidene-3,6-di- O-tosyl- myo-inositol ( 9), 1,2- O-isopropylidene-3,4,6-tri- O-tosyl- myo-inositol ( 10), 1,2:4,5-di- O-isopropylidene-3- O-tosyl- myo-inositol ( 11), 3,6-di- O-benzyl, 1,2:4,5-di- O-isopropylidene- myo-inositol ( 12), 3,6-di- O-benzyl-1,2- O-isopropylidene- myo-inositol ( 13), 3,6-di- O-benzyl- myo-inositol ( 14), 1,2- O-cyclohexylidene- myo-inositol ( 15), 1,2:4,5-di- O-cyclohexylidene- myo-inositol ( 16), 1,2:5,6-di- O-cyclohexylidene- myo-inositol ( 17), 1,3,5- O-(orthoformate)- myo-inositol ( 18) and 2-benzyl-1,3,5- O-(orthoformate)- myo-inositol ( 19). The X-ray diffraction structure of compounds 2, 6-8, 18 and 19 are reported. 相似文献
8.
4 H,6 H-[1,2,5]噁二唑并[3,4- d]嘧啶-5,7-二酮1-氧化物( 1)和6-甲基-4 H,6 H-[1,2,5]噁二唑并[3,4- d]嘧啶-5,7-二酮1-氧化物( 2)是一氧化氮(NO)供体, 将它们分别在无溶剂条件下与高温熔融的全乙酰基保护的核糖、木糖、葡萄糖进行糖基化反应, 分别得到相应的噁二唑并[3, 4- d]嘧啶核苷类化合物 7, 9~ 12, 化合物 7经NH 3-MeOH处理, 去 O-乙酰基制得 8, 这些新型核苷化合物可作为潜在的NO供体. 部分此类化合物的生物活性研究表明, 嘧啶并呋咱核苷衍生物具有抗病毒、抗肿瘤活性, 为研究抗病毒、抗肿瘤药物提供了新结构类型的候选化合物. 相似文献
9.
ABSTRACT Easily accessible 1,6-anhydro-2,3- O-(S)-benzylidene-β-D-mannopyranose was converted in four steps to 1,6-anhydro-3,4-di- O-benzyl-β-D-talopyranose. Glycosylation of the latter with ethyl 2,3,4-tri- O-acetyl-1-thio-α-L-rhamnopyranoside gave, after further processing, 1- O-allyl-3,4-di- O-benzyl-2- O-(2,3,4-tri- O-benzyl-α-L-rhamnopyranosyl)-L-ribitol. 相似文献
10.
Abstract A carboxylate-containing pentasaccharide, methyl O-(β- d-galactopyranosyl)-(1→4)- O-(β- d-glucopyranosyl)-(1→6)- O-{3- O-[( S)-1-carboxyethyl]-β- d-galactopyranosyl-(1→4)- O}-(2-acetamido-2-deoxy-β- d-glucopyranosyl)-(1→3)-β- d-galactopyranoside ( 27) was synthesized by block condensation of suitably protected donors and acceptors. Phenyl 3- O-benzyl-4,6-di- O-chloroacetyl-2-deoxy-2-phthalimido-1-thio-β- d-glucopyranoside ( 17) was condensed with methyl 2,4,6-tri- O-benzyl-β- d-galactopyranoside ( 4) to afford a disaccharide, methyl O-(3- O-benzyl-4,6-di- O-chloroacetyl-2-deoxy-2-phthalimido-β- d-glucopyranosyl)-(1→3)-2,4,6- tri-O-benzyl-β- d-galactopyranoside ( 18). Removal of chloroacetyl groups gave 4,6-diol, methyl 0-(3- O-benzyl-2-deoxy-2-phthalimido-β- d-glucopyranosyl)-(1→3)-2,4,6-tri- O-benzyl-β- d-galactopyranoside ( 19), in which the primary hydroxy group (6-OH) was then selectively chloroacetylated to give methyl O-(3- O-benzyl-6- O-chloroacetyl-2-deoxy-2-phthalimido-β- d-glucopyranosyl)-(1→3)-2,4,6-tri- O-benzyl-β- d-galactopyranoside ( 20). This acceptor was then coupled with 2,4,6-tri- O-acetyl-3- O-[( S)-1-(methoxycarbonyl)ethyl]-α- d-galactopyranosyl trichloroacetimidate ( 14) to afford a trisaccharide, methyl O-{2,4,6-tri- O-acetyl-3- O-[( S)-l-(methoxycarbonyl)ethyl]-β- d-galactopyranosyl}-(1→4)- O-(3- O-benzyl-6- O-chloroacetyl-2-deoxy-2-phthalimido-β- d-glucopyranosyl)-(1→3)-2,4,6-tri- O-benzyl-β- d-galactopyranoside ( 21). Removal of the 6- O-chloroacetyl group in 21 gave 22, which was coupled with 4- O-(2,3,4,6-tetra- O-acetyl-β- d-galactopyranosyl)-2,3,6-tri- O-acetyl-α- d-glucopyranosyl trichloroacetimidate ( 23) to yield protected pentasaccharide 24. Standard procedures were used to remove acetyl groups and the phthalimido group, followed by N-acetylation, and debenzylation to yield pentasaccharide 27 and a hydrazide by-product ( 28) in a 5:1 ratio, respectively. Compound 27 contains a complete repeating unit of the capsular polysaccharide of type III group B Streptococcus in which terminal sialic acid is replaced by an ( S)-1-carboxyethyl group. 相似文献
11.
Abstract 2,3,4,6-Tetra- O-acetyl-D-glucopyranose ( 1) was successfully transformed to an anomeric mixture of 2,3,4,6-tetra- O-acetyl-1- O-(methylthio)thiocarbonyl-D-glucopyranose ( 2) by liquid - liquid and solid - liquid phase transfer methods. Similar anomeric free sugar derivatives bearing acetyl or benzoyl protective groups were also smoothly converted to the corresponding 1- O-(methylthio)thiocarbonyl derivatives. Thermal rearrangement of 1- O-(methylthio)thiocarbonylfuranose derivatives proceeded well to give 1- S-methylthiocarbonyl-1-thiofuranose derivatives. 相似文献
12.
Abstract Four derivatives of β-maltosyl-(1→4)-trehalose were prepared, each with two deoxy functions in one of the constitutive disaccharide building blocks. 2,3-Di- O-acetyl-4,6-dideoxy-4,6-diiodo-α-D-galactopyranosyl- (1→4) ?1,2,3,6-tetra- O-acetyl-D-glucopyranose ( 3) was employed as a precursor for the 4?,6?-dideoxygenated tetrasaccharide 9: coupling of 3 with 2,3,6-tri- O-benzyl-α-D-glucopyranosyl 2,3,6-tri- O-benzylidene-α-D-glucopyranoside ( 4) furnished the tetrasaccharide 5 which was deiodinated and deprotected to yield the target tetrasaccharide 9. Secondly, the dideoxygenated maltose derivative 3-deoxy-4,6- O-isopropylidene-2- O-pivaloyl-β-D-glucopyranosyl- (1→4) ?1,6-anhydro-3-deoxy-2- O-pivaloyl-β-D-glucopyranose ( 10) was ring-opened to the anomeric acetate 11. A [2+2] block synthesis with 4 in TMS triflate mediated glycosylation gave a tetrasaccharide which was deprotected to the 3″,3?-dideoxygenated analogue of β-maltosyl-(1→4)-trehalose. For the third tetrasaccharide, 2,3,2″,3′-tetra- O-benzyl-α,α-trehalose was iodinated at the primary positions and deiodinated in the presence of palladium-on-carbon, then this acceptor was selectively glycosylated with hepta- O-acetyl-maltosyl bromide ( 20). Removal of protective groups furnished the maltosyl trehalose tetrasaccharide deoxygenated at positions C-6 and C-6′. to prepare a 3,3′-dideoxygenated trehalose, the free hydroxyl groups of 2- O-benzyl-4,6- O-( R)-benzylidene-α-D-glucopyranosyl 2- O-benzyl-4,6- O-( R)-benzylidene-α-D-glucopyranoside ( 25) were reduced by Barton-McCombie deoxygenation. One of the benzylidene groups was opened reductively with sodium cyanoborohydride. The resulting free hydroxyl group at the 4′-position was glycosylated in a Koenigs-Knorr reaction with 20 to yield the 3,3′-dideoxygenated tetrasaccharide 32, the fourth target oligosaccharide, after deprotection. 相似文献
13.
ABSTRACT A branched hexasaccharide fragment of type Ia group B streptococcal polysaccharide, α-NeuAc(2→3)-β-D-Gal(1→4)-β-D-GlcNAc(1→3)-[β-D-Glc(1→4)]-β-D-Gal(1→4)-β-D-Glc-OMe ( 13), has been synthesized by chemical-enzymatic procedures. Chemical synthesis of a pentasaccharide, β-D-Gal(1→4)-β-D-GlcNAc(1→3)-[β-D-Glc(1→4)]-β-D-Gal(1→4)-β-D-Glc-OMe ( 12), was achieved from glycosyl donor, 4- O-(2,3,4,6-tetra- O-acetyl-β-D-galactopyranosyl)-3,6-di- O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl trichloroacetimidate ( 9), and acceptor, methyl O-(2,3,4,6-tetra- O-acetyl-β-D-glucopyranosyl)-(1→4)- O-(2,6-di- O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri- O-benzyl-β-D-glucopyranoside ( 6), by block condensation in 41% yield. Following enzymatic sialylation of 12 at the 3- O-position of its terminal galactopyranosyl residue using recombinant α-(2→3)-sialyltransferase and CMP-NeuAc afforded 13 in 59% yield. 相似文献
14.
ABSTRACT The synthesis of several 3-aryl-5-glycosylisoxazole derivatives has been achieved. By condensation of the protected aldehydo-sugars 2,3- O-isopropylidene-D-glyceraldehyde ( 1), 2,3:4,5-di- O-isopropylidene-aldehydo-D-arabinose ( 2) and D-xylose ( 3), and 2,5-anhydro-3,4,5-tri- O-benzoyl-D-mannose ( 4) with benzoylmethylenetriphenylphosphorane, enulose derivatives were formed, which were later converted into a,ß-unsaturated ketoximes. These ketoximes were oxidatively cyclized with iodine and, after removal of the hydroxyl protecting groups, 3-phenyl-5-glycosylisoxazoles were formed. 相似文献
15.
Abstract Reaction of 2- O-unprotected 1- O-silyl-protected D-glucose and D-galactose derivatives 5a-d with benzyl bromide in the presence of sodium hydride as the base afforded 1- O-benzyl 2- O-silyl derivatives 6aα/β - 6dα/β. Thus, prior to anomeric O-benzylation, trans-1,2-silyl group migration takes place. Ensuing removal of the 2- O-silyl group furnishes 2- O-unprotected compounds 8aα/β - 8dα/β, which are useful building blocks. More prone to 1- O-silyl group migration is mannose as shown for derivatives of 4,6- O-benzylidene-D-mannose 9. Cis-1,2- and cis-2,3-silyl group migrations affording compounds 15 and 13 were already observed on deacetylation of the thexyldimethylsilyl 2,3-di- O-acetyl derivative 12β under Zemplén conditions. 相似文献
16.
Abstract 5-Acetamido-3.5-dideoxy- D-galacto-2-octulosonic acid derivatives and the α-2-thioanalog ( 14) were synthesized. Methyl [2-(trimethylsilyl)ethyl 5-acetamido-3,5-dideoxy-α- D-galacto-2-octulopyranosid]onate ( 8), prepared from methyl [2-(trimethylsilyl)ethyl 5-acetamido-3,5-dideoxy- D- glycero-α- D- galacto-2-nonulopyranosid]onate (1) via 8,9- O-isopropylidenation, O-acetylation, O-deisopropylidenation, metaperiodate oxidation, and sodium borohydride reduction, was converted, by selective bromination, into the 8-bromo derivatives ( 9). Compound 12, derived from 8 via O-acetylation and boron trifluoride etherate treatment, was converted to the 2-chloro derivative ( 13), which underwent displacement with potassium thioacetate, to yield methyl 5-acetamido-4,7,8-tri- O-acetyl-2- S-acetyl-2-thio-α-D- galacto-2-octulopyranosonate (14). 相似文献
17.
分别由2-[(2 Z)-3-羧基-1-氧代-2-丙烯基]氨基-2-脱氧-1,3,4,6-四- O-乙酰基- β- D-吡喃葡萄糖( 1a), 2-[(2-羧基苯甲酰基)氨基]-2-脱氧-1,3,4,6-四- O-乙酰基- β- D-吡喃葡萄糖( 2a)和氧化二正丁基锡反应合成了两个新化合物双-{2-[(2 Z)-3-羧基-1-氧代-2-丙烯基]氨基-2-脱氧-1,3,4,6-四- O-乙酰基- β- D-吡喃葡萄糖}-二正丁基锡酯( 1)和双-{2-[(2-羧基苯甲酰基)氨基]-2-脱氧-1,3,4,6-四- O-乙酰基- β- D-吡喃葡萄糖}-二正丁基锡酯( 2), 并经红外光谱、核磁共振( 1H, 13C NMR)、质谱初步确定了其结构. 体外抗肿瘤活性结果表明, 化合物 1对人肺癌细胞株A-549和人肝癌细胞株BEL-7402的细胞毒活性显示为强效; 而对小鼠白血病细胞株P388和人白血病细胞株HL-60的细胞毒活性为弱效. 化合物 2对肿瘤细胞株HL-60, A-549和BEL-7402具有强效的细胞毒活性; 而对肿瘤细胞株P388的作用则为弱效. 克隆基因分析表明化合物 1和 2在3.82×10 -6 和 3.02×10 -6 mol/L均具有造血细胞毒性. 相似文献
18.
Abstract 10- O-(R/S)Tetrahydropyranosyl-β-rhodomycinone ( 5a,b) was prepared via 7,9- O-phenylboronyl-β-rhodomycinone ( 3) from β-rhodomycinone ( 1). Glycosidation of 5a,b with 3,4-di- O-acetyl-1,5-anhydro-2,6-dideoxy- L- arabino-hex-1-enitol (3,4-di- O-acetyl- L-rhamnal) ( 6) and 3,4-di- O-acetyl-1,5-anhydro-2,6-dideoxy- L- lyxo-hex-1-enitol (3,4-di- O-acetyl- L-fucal) ( 7) using N-iodosuccinimide gave the corresponding 7- O-glycosyl-β-rhodomycinones 8a,b, 9a,b and 10a,b, 11a,b. After cleavage of the THP-ether and O-deacetylation 7- O-(2,6-dideoxy-2-iodo-α- L- manno-hexopyranosyl)-β-rhodomycinone ( 14) and 7- O-(2,6-dideoxy-2-iodo-α- L- talo-hexopyranosyl)-β-rhodomycinone ( 16) were obtained. 相似文献
19.
A series of 2,3-diglycosylpyrimidine 4, annelated pyrimidine derivatives, pyrazolo-[3,4- d]pyrimidine 8, ditetrazolo[1,5- a; 1′5′]pyrimidine 9, 2,9a,10-triazaanthracene 12, thieno- [2,3- d]pyrimidine 14, 9-thia-1,3,5,7-tetraazafluorene-8-one 15, 7-oxa-9-thia-1,3,5-triazafluorene-8-one 16, and 5-oxa-9-thia-1,3-diazafluorene 21a , b derivatives have been synthesized via a sequence of heterocyclization reactions of suitably functionalized 6-[5-(4-bromophenyl)oxazol-4-yl]-1,2,3,4-tetrahydro-2-thioxo-4-oxopyrimidine-5-carbonitrile ( 2) with different electrophiles and nucleophiles. The new compounds were prepared with the objective to study their pharmacological properties. 相似文献
20.
Abstract The synthesis of cyclohexyl 2-acetamido-2-deoxy-3- O-{2- O-[2-(guanosine 5′- O-phosphate)ethyl]-α-L-fucopyranosyl}-β-D-glucopyranoside ( 1), a potential inhibitor of α(1→3)fucosyltransferases, is described. Target compound 1 was assembled via fucosylation of cyclohexyl 2-acetamido-2-deoxy-4,6- O-isopropylidene-β-D-glucopyranoside ( 6) with ethyl 2- O-[2-(benzoylhydroxy)ethyl]-3,4- O-isopropylidene-1-thio-β-L-fucopyranoside ( 5) followed by debenzoylation, subsequent condensation of the resulting compound with 3′,4′ -di- O-benzoyl-5′ - O-(2-cyanoethyl- N,N-diisopropylphosphoramidite)-2- N-diphenylacetylguanosine ( 10) and deprotection. 相似文献
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