methyl 4-O-acetyl-3-O-(tert-butyldimethylsilyl)-glucuronate-D-glycal | 351900-87-3

• 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 4-O-acetyl-3-O-(tert-butyldimethylsilyl)-glucuronate-D-glycal
• 英文别名: methyl 4-O-acetyl-3-O-(tert-butyldimethylsilyl)-D-glucuronal；methyl (2S,3R,4R)-3-acetyloxy-4-[tert-butyl(dimethyl)silyl]oxy-3,4-dihydro-2H-pyran-2-carboxylate
• CAS: 351900-87-3
• 化学式: C₁₅H₂₆O₆Si
• 分子量: 330.453
• InChiKey: HVVSTKVEXRXBGY-AGIUHOORSA-N

物化性质

• 沸点：
  351.6±42.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.39
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4-O-acetyl-3-O-(tert-butyldimethylsilyl)-glucuronate-D-glycal 在 2,4,6-三叔丁基吡啶 、 二苯基亚砜 、 氟化氢吡啶 、 trifluoromethanesulfonic acid anhydride 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 吡啶 、 乙醚 、 二氯甲烷 、 氯仿 、 甲苯 为溶剂， 反应 18.7h， 生成 O-4-methoxybenzyl-O-[(2-O-benzoyl-3,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1->2)]-O-[(2,3,4-tri-O-benzoyl-β-D-xylosyl)-(1->3)]-6-O-methyl-4-O-acetyl-β-D-glucuronate
  参考文献：
  名称：

  Synthetic Studies of Complex Immunostimulants from Quillaja saponaria:  Synthesis of the Potent Clinical Immunoadjuvant QS-21A_api

  摘要：

  QS-21 is one of the most promising new adjuvants for immune response potentiation and dose-sparing in vaccine therapy given its exceedingly high level of potency and its favorable toxicity profile. Melanoma, breast cancer, small cell lung cancer, prostate cancer, HIV-1, and malaria are among the numerous maladies targeted in more than 80 recent and ongoing vaccine therapy clinical trials involving QS-21 as a critical adjuvant component for immune response augmentation. QS-21 is a natural product immunostimulatory adjuvant, eliciting both T-cell- and antibody-mediated immune responses with microgram doses. Herein is reported the synthesis of QS-21A(api) in a highly modular strategy, applying novel glycosylation methodologies to a convergent construction of the potent saponin immunostimulant. The chemical synthesis of QS-21 offers unique opportunities to probe its mode of biological action through the preparation of otherwise unattainable nonnatural saponin analogues.

  DOI：

  10.1021/ja062364i
• 作为产物：
  描述：

  (3S,4R)-3,4-Dihydroxy-3,4-dihydro-2H-pyran-2-carboxylic acid methyl ester 在 咪唑 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 4-O-acetyl-3-O-(tert-butyldimethylsilyl)-glucuronate-D-glycal
  参考文献：
  名称：

  Synthesis of the Trisaccharide Portion of the Immunologic Adjuvant QS-21A via Sulfonium-Mediated Oxidative and Dehydrative Glycosylation

  摘要：

  [GRAPHICS]The first synthesis of the trisaccharide fragment of the potent immunologic adjuvant QS-PIA is reported. The key steps involve the application of sulfonium-mediated oxidative and dehydrative glycosidic couplings to construct the anomeric linkages in a short and convergent assembly of the branched trisaccharide.

  DOI：

  10.1021/ol015651u

文献信息

• C2-Hydroxyglycosylation with Glycal Donors. Probing the Mechanism of Sulfonium-Mediated Oxygen Transfer to Glycal Enol Ethers
  作者：Eiji Honda、David Y. Gin

  DOI：10.1021/ja025639c

  日期：2002.6.1

  glycal assembly whereby a hydroxyl functionality is stereoselectively installed at the C2-position of a glycal donor with concomitant glycosylation of a nucleophilic acceptor. Mechanistic investigations into this reaction revealed a novel process for sulfonium-mediated oxidation of glycal enol ethers in which the sulfoxide oxygen atom is stereoselectively transferred to the C2-position of the glycal. (18)O-labeling

  使用二芳基亚砜和三氟甲磺酸酐的试剂组合的 C2-羟基糖基化反应提供了一种新的糖基组装方法，其中羟基官能团立体选择性地安装在糖基供体的 C2 位，伴随着亲核受体的糖基化。对该反应的机理研究揭示了一种锍介导的乙二醇烯醇醚氧化的新过程，其中亚砜氧原子立体选择性地转移到乙二醇的 C2 位。(18)O 标记研究表明，S 到 C2 的氧转移过程涉及 C1[键]O 键的初始形成，然后 O 迁移到 C2，导致中间糖基 1,2-作为原位糖基化剂的脱水吡喃糖苷。