benzyl 2-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside | 146530-59-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzyl 2-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside
• 英文别名: methyl (2S,4aR,6S,7R,8S,8aS)-7-benzoyloxy-8-hydroxy-2-methyl-6-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-2-carboxylate
• CAS: 146530-59-8
• 化学式: C₂₄H₂₆O₉
• 分子量: 458.465
• InChiKey: TWLLJOPGZDMBOZ-SMNHDISXSA-N

物化性质

• 沸点：
  609.1±55.0 °C(predicted)
• 密度：
  1.35±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.82
• 重原子数：
  33.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  109.75
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  benzyl 2-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside 在 palladium on activated charcoal 2,4,6-三甲基吡啶 、 3 A molecular sieve 、 氢气 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 25.0 ℃ 、250.01 kPa 条件下， 反应 10.5h， 生成 O-<2,3-di-O-benzoyl-4,6-O-<(R)-1-(methoxycarbonyl)ethylidene>-α-D-galactopyranosyl>-(1<*>3)-2-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranose
  参考文献：
  名称：

  Synthetic studies toward pyruvate acetal-containing saccharides: En route to the efficient synthesis of Rhizobium-related exopolysaccharide fragments

  摘要：

  The disaccharide building block benzyl O-{2,3-di-O-benzoyl-4,6-O-[(R)-1-(methoxycarbonyl) ethylidene]-beta-D-galactopyranosyl}-(1 --> 3)-2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene] -alpha-D-glucopyranoside (13), related to a Rhizobium exopolysaccharide, was prepared by coupling various 4,6-O-[(R)-1-(methoxycarbonyl)ethylidene]-D-galactosyl donors (benzoyl-protected chloride 1, pivaloyl-protected chloride 2, and benzoyl-protected fluorides 3 and 4, and trichloroacetimidate 5) with benzyl 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-alpha-D-glucopyranoside (10) and the corresponding 2,3-O-tetraisopropyldisiloxane-protected glucoside 12. The best results, with respect to beta-selectivity and yield of the coupling, were obtained with 5 and 10 in dichloromethane. The beta-linked (13) and alpha-linked (14) disaccharides were efficiently converted via the 1-OH derivatives 17 and 21 into the corresponding trichloroacetimidates 18 and 22. The latter were used for the synthesis of the disaccharide ligands 4,6-(R)-pyruvate-beta-D-Galp-(1 --> 3)-4,6-(S)-pyruvate-beta-D-Glcp-O (CH2)(5)NH2 (20), and 4,6-(R)-pyruvate-alpha-D-Galp-(1 --> 3)-4,6-(S)-pyruvate-beta-D-Glcp-O(CH2)(5)NH2 (24). The corresponding tri- and tetra-saccharide derivatives 4,6-(R)-pyruvate-beta-D-Galp-(1 --> 3)-4,6-(S)-pyruvate-beta-D-Glcp-(1 --> 4)-beta-D-Glcp-O(CH2)(5)NH2 (28) and 4,6-(R)-pyruvate-beta-D-Galp-(1 --> 3)-4,6-(S)-pyruvate-beta-D-Glcp-(1 --> 4)-beta-D-Glcp-(1 --> 4)-beta-D-Glcp-O(CH2)(5)NH2 (36) were obtained similarly.

  DOI：

  10.1016/s0008-6215(05)80010-2
• 作为产物：
  描述：

  benzyl 2,3-di-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 24.0h， 生成 benzyl 2-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside
  参考文献：
  名称：

  Synthetic studies toward pyruvate acetal containing saccharides. Synthesis of the carbohydrate part of the Mycobacterium smegmatis pentasaccharide glycolipid and fragments thereof for the preparation of neoantigens

  摘要：

  A series of 2,3-di-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-D-glucopyranosyl donors (beta-phenylthio 3, bromide 4, alpha-chloride 5, beta-fluoride 6, and trichloroacetimidate 7) were prepared from the corresponding alpha-allyl glucoside 1 via the deallylated glucose 2 and were tested in glycosylation reactions with methanol to give the pyruvylated methyl glucosides 8 and 9 and with methyl 2,4,6-tri-O-benzoyl-beta-D-glucopyranoside 10 to give the disaccharide 11. Best results with respect to yield and beta-selectivity of the coupling were achieved with imidate 7. Thus, the 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-3-O-methyl-D-glucopyranosyl trichloroacetimidate 14 was prepared from its benzyl glucoside 12 and used for the synthesis of fragments related to the Mycobacterium smegmatis lipopentasaccharide. Trimethylsilyl trifluoromethanesulfonate-mediated condensation of 14, 5-[(benzyloxycarbonyl)amino]pentanol, and 10, respectively, followed by deblocking of the products 15 and 17 gave the pyruvylated aminopentyl glucoside 16 and methyl laminaribioside 18. Treatment of 17 with dichloromethyl methyl ether gave the laminaribiosyl chloride 19, coupling of which with protected 5-aminopentanol gave 20 also obtained from 14 and the monosaccharide nucleophile 26. The trisaccharide 5-aminopentyl glycoside fragment 42 was prepared by first coupling of 14 and benzyl 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-alpha-D-glucopyranoside 30 that was converted to the bispyruvylated laminaribiose imidate 33, followed by condensation with thioglycoside 38 obtainable in four steps from 1,2,4,6-tetra-O-acetyl-3-O-benzyl-beta-D-glucopyranose to give the trisaccharide ethyl thioglycoside 40. Next, NIS-mediated condensation of 40 and 5-[(benzyloxycarbonyl)amino]pentanol followed by deblocking gave 42. Pentasaccharide 45 was similarly prepared from 40 and hepta-O-benzoyltrehalose 43 to give first the blocked saccharide 44, deblocking of which afforded the target pentasaccharide.

  DOI：

  10.1021/jo00057a021

文献信息

• Rhizobial saccharides. Part. 4. Unusual Reactivity of Pyruvated Glycosyl Donors during construction of rhizobial exopolysaccharide fragments
  作者：Thomas Ziegler、Elisabeth Eckhardt

  DOI：10.1002/prac.19973390196

  日期：——

  Two pyruvated galactosyl donors, 2,3-di-O-benzoyl-4,6-0-[1-(R)-methoxycarbonyl(ethylidene)]-alpha-D-galactopyranosyl chloride (6) and trichloroacetimidate 13, were coupled to position 3 of suitably protected mono and disaccharide benzyl glucoside accepters. For both donors, an unusual high content of the alpha-(1-->3)-linked products was obtained. The corresponding beta-(1-->3)-linked di- and trisaccharides are related to exopolysaccharides of Rhizobium leguminosarum.