3-O-trimethylsilyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose | 3067-62-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-O-trimethylsilyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
• 英文别名: 1,2:5,6-di-O-isopropylidene-3-O-(trimethylsilyl)-α-D-glucofuranose；{[(3aR,5R,6S,6aR)-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-yl]oxy}trimethylsilane；[(3aR,5R,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl]oxy-trimethylsilane
• CAS: 3067-62-7
• 化学式: C₁₅H₂₈O₆Si
• 分子量: 332.469
• InChiKey: IESPVZGLCPEFNL-UJPOAAIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.23
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-O-trimethylsilyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 在 poly(4-vinylpyridine)-supported FeCl₃ 、 水 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.5h， 以92%的产率得到(R)-1-((3aR,5R,6S,6aR)-2,2-Dimethyl-6-trimethylsilanyloxy-tetrahydro-furo[2,3-d][1,3]dioxol-5-yl)-ethane-1,2-diol
  参考文献：
  名称：

  Polymer-Supported Ferric Chloride as a Heterogeneous Catalyst for Chemoselective Deprotection of Acetonides

  摘要：

  乙酰氨基化合物在室温下使用以聚乙烯吡咯烷酮（PVP）为支持体的氯化铁作为异相催化剂，在乙腈-二氯甲烷中进行化学选择性脱保护，获得相应的1,2-二醇，产率极高。

  DOI：

  10.1055/s-2005-861817
• 作为产物：
  描述：

  3-O-[(t-butyl)dimethylsilyl]-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 在 potassium fluoride 、 四丁基溴化铵 作用下， 以 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 0.28h， 生成 3-O-trimethylsilyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  RAPID CARBOHYDRATE PROTECTING GROUP MANIPULATIONS ASSISTED BY MICROWAVE DIELECTRIC HEATING

  摘要：

  The protocols for oligosaccharide synthesis are often tedious due to extended synthetic routes and reaction times. We herein describe methods assisted by microwave dielectric heating, which enable very short reaction times and high yields for the introduction and removal of eleven of the most commonly used protecting groups in carbohydrate syntheses. Several examples are reported, where solid supported reagents in combination with microwave dielectric heating have been used. This results in both faster and easier synthesis and purification.

  DOI：

  10.1081/car-100105712

文献信息

• A General Approach to <i>O</i> ‐Sulfation by a Sulfur(VI) Fluoride Exchange Reaction
  作者：Chao Liu、Cangjie Yang、Seung Hwang、Samantha L. Ferraro、James P. Flynn、Jia Niu

  DOI：10.1002/anie.202007211

  日期：2020.10.12

  scalable and facile synthesis of complex bioactive molecules carrying O‐sulfates remains challenging. Reported here is a general approach to O‐sulfation by the sulfur(VI) fluoride exchange (SuFEx) reaction between aryl fluorosulfates and silylated hydroxy groups. Efficient sulfate diester formation was achieved through systematic optimization of the electronic properties of aryl fluorosulfates. The versatility

  O-硫酸化是生物活性分子中广泛存在的重要化学代码，但携带 O-硫酸盐的复杂生物活性分子的可扩展和简便合成仍然具有挑战性。这里报道的是通过芳基氟硫酸盐和甲硅烷基化羟基之间的硫 (VI) 氟化物交换 (SuFEx) 反应进行 O-硫酸化的一般方法。通过对芳基氟硫酸盐的电子特性进行系统优化，实现了有效的硫酸二酯形成。这种 O-硫酸化策略的多功能性在各种复杂分子的可扩展合成中得到证明，这些分子在不同位置携带硫酸二酯，包括单糖、二糖、氨基酸和类固醇。从硫酸二酯中选择性水解和氢解去除芳基掩蔽基团，以优异的产率得到相应的 O-硫酸盐产物。该策略为合成 O-硫酸盐生物活性化合物提供了强大的工具。
• Indium Tribromide: An Efficient Catalyst for the Silylation of Hydroxy Groups by the Activation of Hexamethyldisilazane
  作者：J. Yadav、B. Reddy、A. Basak、G. Baishya、A. Narsaiah

  DOI：10.1055/s-2006-950322

  日期：2006.11

  A variety of substrates containing hydroxy groups have been protected as their corresponding trimethylsilyl ethers using 1,1,1,3,3,3-hexamethyldisilazane in the presence of indium tribromide. The catalyst indium tribromide activates the 1,1,1,3,3,3-hexa­methyldisilazane and accelerates the reaction under mild reaction conditions at room temperature.

  多种含有羟基的底物已在三甲基硅醚的对应物中被保护，使用了在溴化铟存在下的1,1,1,3,3,3-己六甲基二硅氮。催化剂溴化铟激活了1,1,1,3,3,3-己六甲基二硅氮，并在室温的温和反应条件下加速反应。
• Facile Method for Trimethylsilylation of Alcohols using Hexamethyldisilazane and Ammonium Thiocyanate under Neutral Conditions
  作者：Vrushali H. Jadhav、K. S. Ajish Kumar、Vinod D. Chaudhari、Dilip D. Dhavale

  DOI：10.1080/00397910701227440

  日期：2007.4.1

  A highly efficient method for trimethylsilylation of primary, secondary, tertiary, allylic, and a variety of sugar-derived alcohols using hexamethyldisilazane in the presence of a catalytic amount of ammonium thiocyanate under neutral conditions is reported.
• RAPID CARBOHYDRATE PROTECTING GROUP MANIPULATIONS ASSISTED BY MICROWAVE DIELECTRIC HEATING
  作者：Eva Söderberg、Jacob Westman、Stefan Oscarson*

  DOI：10.1081/car-100105712

  日期：2001.6.30

  The protocols for oligosaccharide synthesis are often tedious due to extended synthetic routes and reaction times. We herein describe methods assisted by microwave dielectric heating, which enable very short reaction times and high yields for the introduction and removal of eleven of the most commonly used protecting groups in carbohydrate syntheses. Several examples are reported, where solid supported reagents in combination with microwave dielectric heating have been used. This results in both faster and easier synthesis and purification.
• Polymer-Supported Ferric Chloride as a Heterogeneous Catalyst for Chemoselective Deprotection of Acetonides
  作者：M. Chari、K. Syamasundar

  DOI：10.1055/s-2005-861817

  日期：——

  Acetonides undergo chemoselective deprotection to afford the corresponding 1,2-diols in excellent yields using polymer (PVP)-supported ferric chloride as a heterogeneous catalyst in acetonitrile-dichloromethane at room temperature.

  乙酰氨基化合物在室温下使用以聚乙烯吡咯烷酮（PVP）为支持体的氯化铁作为异相催化剂，在乙腈-二氯甲烷中进行化学选择性脱保护，获得相应的1,2-二醇，产率极高。