methyl 4β-(2,3,4,6-tetra-O-pivaloylglucopyranosyl)-2,3,6-tri-O-benzyl-α-glucopyranoside

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 4β-(2,3,4,6-tetra-O-pivaloylglucopyranosyl)-2,3,6-tri-O-benzyl-α-glucopyranoside
• 英文别名: methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyl)-α-D-glucopyranoside；pivaloyl(-2)[pivaloyl(-3)][pivaloyl(-4)][pivaloyl(-6)]Glc(b1-4)[Bn(-2)][Bn(-3)][Bn(-6)]a-Glc1Me；[(2R,3R,4S,5R,6S)-3,4,5-tris(2,2-dimethylpropanoyloxy)-6-[(2R,3R,4S,5R,6S)-6-methoxy-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl 2,2-dimethylpropanoate
• 化学式: C₅₄H₇₄O₁₅
• 分子量: 963.173
• InChiKey: MSGZHBABVROPDJ-KJIMUUKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  69
• 可旋转键数：
  26
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  170
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为产物：
  描述：

  2,3,4,6-O-四特戊酰基-alpha-D-溴代吡喃葡萄糖 在 三氟甲磺酸三甲基硅酯 、 4 Angstroem MS 作用下， 以 氯仿 、 乙腈 为溶剂， 反应 27.08h， 生成 methyl 4β-(2,3,4,6-tetra-O-pivaloylglucopyranosyl)-2,3,6-tri-O-benzyl-α-glucopyranoside
  参考文献：
  名称：

  The Chemistry of Isopropenyl Glycopyranosides. Transglycosylations and Other Reactions

  摘要：

  Various anomerically pure isopropenyl alpha- and beta-glycopyranosides have been synthesized and shown to undergo synthetically useful transglycosylation reactions with a variety of primary and secondary carbohydrate alcohols. Although stable when stored, isopropenyl glycosides are readily activated as glycosyl donors by a variety of electrophiles, including N-iodosuccinimide/triflic acid, trimethylsilyl triflate, and triflic anhydride. Under conditions that retard formation of the glycosyl cation, the reactivity of isopropenyl glycosides is diverted away from transglycosylation and toward electrophilic addition across the vinyl ether double bond.

  DOI：

  10.1021/jo960190p

文献信息

• Glycosyl transfer by isopropenyl glycosides: Trisaccharide synthesis in one pot by selective coupling of isopropenyl and n-pentenyl glycopyranosides
  作者：H.Keith Chenault、Alfredo Castro

  DOI：10.1016/0040-4039(94)88449-8

  日期：1994.12

  O-Isopropenyl glycosides bearing ester protecting groups are activated as glycosyl donors by a variety of electrophiles. Diastereomerically pure β-glycoside products are formed in good yields. Selective activation of O-isopropenyl 2,3,4,6-tetra-O-pivaloyl-β-glucopyranoside in the presence of O-pent-4-enyl 2,3,4,6-tetra-O-benzyl-β-glucopyranoside allows two successive glycosyl couplings to be performed

  带有酯保护基的O-异丙烯基糖苷被各种亲电试剂活化为糖基供体。非对映体纯的β-糖苷产物以良好的产率形成。在O-戊-4-烯基2,3,4,6-四-O-苄基-β-存在下的O-异丙烯基2,3,4,6-四-O-新戊酰基-β-吡喃葡萄糖苷的选择性活化吡喃葡萄糖苷可以在一个罐中进行两个连续的糖基偶联，从而以25％的收率得到三糖。
• Lauryl and Stearyl Thioglycosides: Preparation and Reactivity of the Glycosyl Donor
  作者：Hideaki Matsui、Jun-ichi Furukawa、Takuro Awano、Norio Nishi、Nobuo Sakairi

  DOI：10.1246/cl.2000.326

  日期：2000.4

  Lauryl and stearyl thioglycosides were prepared by the Lewis acid catalyzed reaction of 1-O-acetylated sugars with non-volatile and almost odorless 1-dodecanethiol and 1-octadecanethiol, respectively. These thioglycosides were activated by N-iodosuccinimide-TfOH to glycosyl donors producing disaccharides in good yields.

  月桂醇和硬脂醇硫糖苷是通过路易斯酸催化的反应制备的，该反应涉及1-O-乙酰化糖与非挥发性和几乎无气味的壬基硫醇和十八烷硫醇。将这些硫糖苷用N-碘琥珀酰亚胺-TfOH激活，生成优良产率的二糖供体。
• Catalytic Decarboxylative Glycosylation Promoted by Hafnium(IV) ­Trifluoromethanesulfonate: β-Selective Glycosylation via a Mixed Carbonate of an Acyl-Protected Donor Sugar
  作者：Shiro Ikegami、Isao Azumaya、Masaomi Kotani

  DOI：10.1055/s-2004-822885

  日期：——

  Acyl-protected mixed carbonates were effectively decarboxylated by catalytic amounts (2-5 mol%) of hafnium(IV) trifluoromethanesulfonate in dichloromethane at room temperature to give the corresponding β-glycosides in excellent yields.

  酰基保护的混合碳酸酯在室温下通过催化量（2-5 mol%）的三氟甲磺酸铪（IV）在二氯甲烷中有效脱羧，以优异的产率得到相应的β-糖苷。
• An efficient synthesis of mixed β-carbonates of acyl-protected sugar and their decarboxylative glycosidation promoted by trimethylsilyl trifluoromethanesulfonate
  作者：Isao Azumaya、Toshihiro Niwa、Masaomi Kotani、Takamasa Iimori、Shiro Ikegami

  DOI：10.1016/s0040-4039(99)00843-6

  日期：1999.6

  Mixed beta-carbonates of acyl-protected sugar are stereoselectively prepared by using an N-succinimidyl group for activation of the acceptor alcohol carbonate. The glycosyl carbonates are smoothly decarboxylated by trimethylsilyl trifluoromethanesulfonate (Me3SiOTf) to give beta-glycosides preferentially in high yields. (C) 1999 Elsevier Science Ltd. All rights reserved.
• 2-Pyridyl glycoside: an alternative glycosyl donor in preactivation protocol
  作者：De-Cai Xiong、An-Qi Yang、Yang Yu、Xin-Shan Ye

  DOI：10.1016/j.tetlet.2014.11.066

  日期：2015.1

  2-Pyridyl glycosides have been identified to be powerful glycosyl donors for the preactivation-based oligosaccharide synthesis. By using stoichiometric amount of Tf2O, the 2-pyridyl glycosides were pre-activated, which subsequently underwent glycosylation reactions smoothly to produce the coupled products in high yields. Furthermore, the 2-pyridyl glycosides were applied to the efficient oligosaccharide assembly by the preactivation-based one-pot oligosaccharide synthesis protocol. (C) 2014 Elsevier Ltd. All rights reserved.