benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside | 145835-75-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside
• CAS: 145835-75-2
• 化学式: C₁₇H₂₂O₈
• 分子量: 354.357
• InChiKey: RSNHQCBIGQJKLZ-MMCSFCSJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.05
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  103.68
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside 在 palladium on activated charcoal 吡啶 、 三氟甲磺酸三甲基硅酯 、 氢气 、 potassium carbonate 、 苯甲酰氯 作用下， 以 二氯甲烷 、 溶剂黄146 、 乙酸乙酯 为溶剂， 20.0~25.0 ℃ 、101.01 kPa 条件下， 反应 95.0h， 生成 O-<2-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-3-O-methyl-β-D-glucopyranosyl>-(1<*>3)-2-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-D-glucopyranose trichloroacetamidate
  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
• 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 甲醇 作用下， 反应 24.0h， 以85%的产率得到benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside
  参考文献：
  名称：

  使用TIPS保护的糖苷构建寡糖的新型融合策略。耻垢分枝杆菌糖脂相关片段的合成

  摘要：

  将4，6- O-丙酮酸化的葡糖苷1分别转化为相应的葡糖基氟化物3和2，3 - O -TIPS保护的葡糖吡喃糖苷5。3和5的路易斯酸催化的偶合提供了丙酮酸化的二糖6，其中之一通过二糖供体8被进一步转化为耻垢分枝杆菌的二糖和三糖片段。

  DOI：

  10.1016/s0040-4039(00)60999-1

文献信息

• Synthetic studies toward pyruvate acetal-containing saccharides: En route to the efficient synthesis of Rhizobium-related exopolysaccharide fragments
  作者：Elisabeth Eckhardt、Thomas Ziegler

  DOI：10.1016/s0008-6215(05)80010-2

  日期：1994.11

  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.