methyl 3-O-(tert-butyldimethylsilyl)-D-glucuronal | 351900-86-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: methyl 3-O-(tert-butyldimethylsilyl)-D-glucuronal
• 英文别名: methyl 3-O-(tert-butyldimethylsilyl)-glucuronate-D-glycal；methyl (2S,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-3,4-dihydro-2H-pyran-2-carboxylate
• CAS: 351900-86-2
• 化学式: C₁₃H₂₄O₅Si
• 分子量: 288.416
• InChiKey: YUIAXNQPLIJZIA-VWYCJHECSA-N

物化性质

• 沸点：
  335.0±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)：
  1.82
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3-O-(tert-butyldimethylsilyl)-D-glucuronal 在 4-二甲氨基吡啶 、 2,4,6-三叔丁基吡啶 、 二苯基亚砜 、 trifluoromethanesulfonic acid anhydride 作用下， 以 二氯甲烷 为溶剂， 反应 4.4h， 生成 methyl 1,2-anhydro-4-O-acetyl-3-O-(tert-butyldimethylsilyl)-α-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：

  (2S,3S,4R)-3,4-二乙酰氧基-3,4-二氢-2H-吡喃-2-羧酸甲酯 在 咪唑 、 sodium methylate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 methyl 3-O-(tert-butyldimethylsilyl)-D-glucuronal
  参考文献：
  名称：

  除草剂 B 的首次合成。通过使用吡喃糖环上相邻大块甲硅烷基保护基团之间的空间排斥的构象限制策略立体选择性构建三环未脱糖部分†

  摘要：

  实现了核苷类抗生素除草素 B (1b) 的首次全合成，其中以二碘化钐 (SmI2) 促进的新型羟醛型 C-糖苷化反应为关键步骤。在 THF 中用 SmI2 处理 3,4-O-(1,1,3,3-四异丙基-1,3-二硅氧烷二基)-1-苯硫基-2-ulos-β-d-葡萄糖醛酸甲酯 (13) 区域选择性地得到相应的 1-烯醇化物，它很容易被 1-β-d-木糖基腺嘌呤 5'-醛衍生物 7 捕获，得到产物 19a，b，为异头混合物。使用 Burgess 内盐对 19a,b 中的 5'-羟基进行脱水得到烯酮 20，随后将其氢化得到十一碳呋喃酮基腺嘌呤衍生物 21。21 的脱保护得到三环糖核苷 23。然而，它是6' 位的除草剂 B。通过使用基于吡喃糖环上相邻大保护基团之间排斥的构象限制策略来构建所需的 6'-α-构型。因此，当甲基 3-O-叔...

  DOI：

  10.1021/ja992608h

文献信息

• The First Synthesis of Herbicidin B. Stereoselective Construction of the Tricyclic Undecose Moiety by a Conformational Restriction Strategy Using Steric Repulsion between Adjacent Bulky Silyl Protecting Groups on a Pyranose Ring
  作者：Satoshi Ichikawa、Satoshi Shuto、Akira Matsuda

  DOI：10.1021/ja992608h

  日期：1999.11.1

  The first total synthesis of the nucleoside antibiotic herbicidin B (1b) was achieved, where a novel aldol-type C-glycosidation reaction promoted by samarium diiodide (SmI2) was used as a key step. Treatment of methyl 3,4-O-(1,1,3,3-tetraisopropyl-1,3-disiloxanediyl)-1-phenylthio-2-ulos-β-d-glucuronate (13) with SmI2 in THF regioselectively gave the corresponding 1-enolate, which was readily trapped

  实现了核苷类抗生素除草素 B (1b) 的首次全合成，其中以二碘化钐 (SmI2) 促进的新型羟醛型 C-糖苷化反应为关键步骤。在 THF 中用 SmI2 处理 3,4-O-(1,1,3,3-四异丙基-1,3-二硅氧烷二基)-1-苯硫基-2-ulos-β-d-葡萄糖醛酸甲酯 (13) 区域选择性地得到相应的 1-烯醇化物，它很容易被 1-β-d-木糖基腺嘌呤 5'-醛衍生物 7 捕获，得到产物 19a，b，为异头混合物。使用 Burgess 内盐对 19a,b 中的 5'-羟基进行脱水得到烯酮 20，随后将其氢化得到十一碳呋喃酮基腺嘌呤衍生物 21。21 的脱保护得到三环糖核苷 23。然而，它是6' 位的除草剂 B。通过使用基于吡喃糖环上相邻大保护基团之间排斥的构象限制策略来构建所需的 6'-α-构型。因此，当甲基 3-O-叔...
• Synthesis of the Trisaccharide Portion of the Immunologic Adjuvant QS-21A via Sulfonium-Mediated Oxidative and Dehydrative Glycosylation
  作者：Yong-Jae Kim、David Y. Gin

  DOI：10.1021/ol015651u

  日期：2001.6.1

  [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.
• Synthetic Studies of Complex Immunostimulants from <i>Quillaja saponaria</i>:  Synthesis of the Potent Clinical Immunoadjuvant QS-21A_a_pi
  作者：Yong-Jae Kim、Pengfei Wang、Mauricio Navarro-Villalobos、Bridget D. Rohde、DerryBerry、David Y. Gin

  DOI：10.1021/ja062364i

  日期：2006.9.1

  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.