methyl 2,3-di-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-β-D-glucopyranoside | 138857-66-6

• 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: methyl 2,3-di-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-β-D-glucopyranoside
• 英文别名: methyl 2,3-di-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-β-D-glucopyranoside；methyl (2S,4aR,6R,7R,8S,8aR)-7,8-dibenzoyloxy-6-methoxy-2-methyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-2-carboxylate
• CAS: 138857-66-6
• 化学式: C₂₅H₂₆O₁₀
• 分子量: 486.475
• InChiKey: NZQHUAORXGMFAI-LDZRUQOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.11
• 重原子数：
  35.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  115.82
• 氢给体数：
  0.0
• 氢受体数：
  10.0

反应信息

• 作为产物：
  描述：

  苯甲酰溴 在 吡啶 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 methyl 2,3-di-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-β-D-glucopyranoside
  参考文献：
  名称：

  Convenient Synthesis of 4,6-O-Pyruvate Acetal Containing Glycosides via Tetraisopropyldisiloxanediyl Protected Sugars

  摘要：

  烷基 D-吡喃葡糖苷和烷基或苯基1-硫-ß-D-吡喃葡糖苷 1 与1,3-二氯-1,1,3,3-四异丙基二硅氧烷反应，得到相应的4,6-O-(1,1,3,3-四异丙基二硅氧烷-1,3-二基)保护的糖苷 2，随后用苯甲酰溴进行苯甲酰化，得到完全保护的糖苷 3。后者与丙酮酸甲酯和少量三甲基硅基三氟甲磺酸酯反应，以高非对映选择性得到烷基和苯基4,6-O-[1-(甲氧羰基)乙叉]吡喃葡糖苷 4。

  DOI：

  10.1055/s-1992-26291

文献信息

• 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
  作者：Thomas Ziegler、Elisabeth Eckhardt、Veronique Birault

  DOI：10.1021/jo00057a021

  日期：1993.2

  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.
• Ziegler, Thomas; Eckhardt, Elisabeth; Herold, Gerhard, Liebigs Annalen der Chemie, 1992, # 5, p. 441 - 452
  作者：Ziegler, Thomas、Eckhardt, Elisabeth、Herold, Gerhard

  DOI：——

  日期：——