benzyl 2,3-di-O-benzoyl-α-D-glucopyranoside | 65725-43-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzyl 2,3-di-O-benzoyl-α-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-5-benzoyloxy-3-hydroxy-2-(hydroxymethyl)-6-phenylmethoxyoxan-4-yl] benzoate
• CAS: 65725-43-1；138857-51-9；65725-42-0
• 化学式: C₂₇H₂₆O₈
• 分子量: 478.499
• InChiKey: FOQXIPSGVFBZOB-CXBVJKJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  benzyl 2,3-di-O-benzoyl-α-D-glucopyranoside 在 咪唑 、 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 3.5h， 生成 benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-2,3-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-α-D-glucopyranoside
  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：

  [(4aR,6S,7R,8S,8aR)-7-benzoyloxy-2-phenyl-6-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] benzoate 在 溶剂黄146 作用下， 反应 4.0h， 以68%的产率得到benzyl 2,3-di-O-benzoyl-α-D-glucopyranoside
  参考文献：
  名称：

  Chondroitin-4-O-sulfatase from Bacteroides thetaiotaomicron: exploration of the substrate specificity

  摘要：

  Bacterial sulfatases can be good tools to increase the molecular diversity of glycosaminoglycan synthetic fragments. A chondroitin 4-O-sulfatase from the human commensal bacterium Bacteroides thetaiotaomicron has recently been identified and expressed. In order to use this enzyme for synthetic purposes, the minimal structure required for its activity has been determined. For that, four 4-O-sulfated monosaccharides and one 4-O-sulfated disaccharide have been synthesized and used as substrates with the sulfatase. The minimum structure was shown to be a disaccharide but in contrast to the natural substrate, which must have a 4,5-insaturation, the enzyme accepts as substrate, a disaccharide with a saturated glucuronic acid at the non-reducing end and even a glucopyranosyl moiety without the carboxylic acid functionality. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2012.03.033

文献信息

• Rhizobial saccharides 2. Selective synthesis of both diastereomers of 4,6-O-pyruvylated d-glycopyranosides
  作者：Thomas Ziegler

  DOI：10.1016/0040-4039(94)85023-2

  日期：1994.9

  Both diastereomers of 4,6-O-pyruvylated glycosides S- and R - 2 were selectively prepared from the corresponding 4,6-unprotected glycosides 1 by acetalation of the latter with methyl pyruvate and BF3-diethylether complex. In acetonitrile as the solvent, the thermodynamically favoured diastereomers having an axial-oriented methoxycarbonyl group are formed preferentially. In methyl pyruvate as the solvent

  的4,6-非对映体两者ø -pyruvylated苷小号和- [R - 2从相应的4,6-未受保护的糖苷选择性地制备1由后者的缩醛化用丙酮酸甲酯和BF 3 -diethylether复杂。在乙腈作为溶剂中，优先形成具有轴向取向的甲氧基羰基的热力学上有利的非对映异构体。在作为溶剂的丙酮酸甲酯中，具有赤道取向的甲氧基羰基的非对映异构体是主要产物，并且缩醛化的非对映选择性受起始糖苷1的2-O和3-O位置上的保护基的影响。
• Diastereoselective formation of pyruvylated glycosides from partly protected sugars and methyl pyruvate
  作者：Thomas Ziegler、Elisabeth Eckhardt、Gerhard Herold

  DOI：10.1016/s0040-4039(00)60097-7

  日期：1992.7

  Various partly protected sugars (gluco-, manno-, and galactopyranosides) were acetalized with methyl pyruvate in moderate to good yield with BF3-etherate as the condensing reagent. Thus, (1-methoxycarbonyl)ethylidene glycosides were obtained diastereoselectivity.

  各种部分受保护的糖（葡萄糖基，甘露糖苷和半乳糖吡喃糖苷）以丙酮酸甲酯缩醛化，并以BF 3-醚酸酯为缩合试剂。因此，获得了（1-甲氧基羰基）亚乙基糖苷的非对映选择性。
• ——
  作者：Gregor Lemanski、Thomas Ziegler

  DOI：10.1002/1522-2675(20001004)83:10<2655::aid-hlca2655>3.0.co;2-u

  日期：2000.10.4

  A series of prearranged glycosides 5, 17, 23, 28, 37 and 41, having a benzyl-protected 1-thiomannosyl donor linked through its positions 2, 3, 4 and 6 via succinate and malonate tethers, respectively, to positions 2, 3, and 6 of a benzyl glucopyranoside acceptor, were prepared by condensation of the respective mannosyl succinates and malonates with suitably protected benzyl glucopyranosides. The prearranged glycosides were intramolecularly coupled under various conditions to give the corresponding, tethered (1 --> 4)-linked disaccharides The yields and anomer ratios of the products of these couplings were interpreted in terms of the thermodynamic stability of the resulting disaccharides. In the case of prearranged glycoside 17, having positions 3 of both the donor and the acceptor linked by a succinate tether, a strong dependence of the diastereoselectivity of the intramolecular glycosylation on the activation procedure was observed. All other cases did not show a significant dependence of the outcome of the anomeric configuration in intramolecular glycosylation on the activation procedure or the solvent.