methyl 2,3-di-O-allyl-6-O-benzyl-α-D-glucopyranoside | 58341-69-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3-di-O-allyl-6-O-benzyl-α-D-glucopyranoside
• 英文别名: 1-O-methyl-2,3-di-O-allyl-6-O-benzyl-α-D-glucopyranose；(2R,3R,4S,5R,6S)-6-methoxy-2-(phenylmethoxymethyl)-4,5-bis(prop-2-enoxy)oxan-3-ol
• CAS: 58341-69-8
• 化学式: C₂₀H₂₈O₆
• 分子量: 364.439
• InChiKey: QAGKDMDUTFFFTB-OBKDMQGPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-allyl-6-O-benzyl-α-D-glucopyranoside 在 氢氧化钾 、 四丁基硫酸氢铵 作用下， 以 四氢呋喃 为溶剂， 反应 12.75h， 生成 2-[2-[2-[2-[2-[2-[(2R,3R,4S,5R,6S)-6-methoxy-2-(phenylmethoxymethyl)-4,5-bis(prop-2-enoxy)oxan-3-yl]oxyethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol
  参考文献：
  名称：

  Chirale Kronenether mit integriertem 1,4-verbrückten d-Glucopyranose-Baustein

  摘要：

  含 1,4-连接的 d-吡喃葡萄糖分子的碳水化合物冠醚

  DOI：

  10.1055/s-1998-4480
• 作为产物：
  描述：

  (2R,4aR,6S,7R,8S,8aR)-6-methoxy-2-phenyl-7,8-bis(prop-2-enoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine 在 三乙基硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以92%的产率得到methyl 2,3-di-O-allyl-6-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  HClO4–silica-catalysed regioselective opening of benzylidene acetals and its application towards regioselective HO-4 glycosylation of benzylidene acetals in one-pot

  摘要：

  Here we report a high-yielding method for the regioselective reductive ring opening of 4,6-O-benzylidene acetals of hexapyranosides using inexpensive and robust HClO4-SiO2 as the acidic catalyst and triethyl-silane as the hydride donor. Under the optimized condition, gluco-and mannopyranosides give the respective 6-O-benzyl derivative in good to excellent yields while the corresponding galactopyranoside gives the corresponding 6-O-benzyl derivative in lower yield. As the optimized condition involves acidic catalyst, we also successfully developed further application of the present method for the tandem regioselective opening and glycosylation in one-pot. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2014.01.011

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。
• Stereospecific Furanosylations Catalyzed by Bis-thiourea Hydrogen-Bond Donors
  作者：Andrew B. Mayfield、Jan B. Metternich、Adam H. Trotta、Eric N. Jacobsen

  DOI：10.1021/jacs.0c00335

  日期：2020.2.26

  We report a new method for stereoselective O-furanosylation reactions promoted by a precisely tailored bis-thiourea hydrogen-bond-donor catalyst. Furanosyl donors outfitted with an anomeric dialkylphosphate leaving group undergo substitution with high anomeric selectivity, providing access to the challenging 1,2-cis substitution pattern with a range of alcohol acceptors. A variety of stereochemically distinct, benzyl-protected glycosyl donors were engaged successfully as substrates. Mechanistic studies support a stereospecific mechanism in which rate-determining substitution occurs from a catalyst-donor resting-state complex.