methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-D-galactopyranosyl)-α-D-glucopyranoside | 194208-51-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-D-galactopyranosyl)-α-D-glucopyranoside
• 英文别名: Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Gal(?1-4)[Bn(-2)][Bn(-3)][Bn(-6)]a-Glc1Me；(2S,3R,4S,5R,6R)-2-methoxy-3,4-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-5-[(3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxyoxane
• CAS: 194208-51-0
• 化学式: C₆₂H₆₆O₁₁
• 分子量: 987.199
• InChiKey: XGUQGDPCAPRZDC-XCYSWQIDSA-N

物化性质

• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  73
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为产物：
  描述：

  prop-2-ynyl 2,3,4,6-tetra-O-benzyl-β-D-galactopyranoside 在 4 A molecular sieve 、 三氟化硼乙醚 、 mercury(II) trifluoroacetate 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 23.0h， 生成 methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-D-galactopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Design, Development and Utility of Glycosyl Donors Bearing an Acetoxymethoxy Leaving Group

  摘要：

  已制备新型糖苷供体 2d、4d 和 6d，具有“乙酰氧基-甲氧基”离去基团，并通过将其与醇 A-G 结合，利用 BF3-Et2O 作为促使剂，展示了它们的实用性，从而获得了二糖和三糖。

  DOI：

  10.1246/cl.1998.863

文献信息

• Glycosyl Phosphonium Halide as a Reactive Intermediate in Highly α-Selective Glycosylation
  作者：Yohei Kobashi、Teruaki Mukaiyama

  DOI：10.1246/bcsj.78.910

  日期：2005.5

  Highly α-selective glycosylations of several glycosyl acceptors with 2,3,4,6-tetra-O-benzyl-d-glucopyranosyl bromide (4) proceeded smoothly in the presence of tri(1-pyrrolidino)phosphine oxide in CH2Cl2 at room temperature or in refluxing CHCl3 via glycosyl phosphonium bromide intermediates and the corresponding disaccharides were afforded in good yields with high selectivities. Further, the one-pot glycosylation starting from glycosyl acetate using iodotrimethylsilane and phosphine oxide also proceeded efficiently in CH2Cl2 at room temperature to give the corresponding disaccharides, although this one-pot synthesis of α-glycoside via in situ anomerization procedure is considered difficult because glycosyl halide reacts with trimethylsilyl acetate easily to regenerate glycosyl acetate, a starting glycosyl donor.

  在常温下或在回流的氯仿中，以三（1-吡咯烷基）磷氧化物为催化剂，2,3,4,6-四-O-苄基-d-葡萄糖吡喃糖溴化物（4）与几种糖苷受体的高选择性α-糖苷化反应顺利进行，生成相应的二糖，收率良好且选择性高。此外，使用碘三甲基硅烷和磷氧化物从糖苷醋酸酯进行的一锅法糖苷化反应也在常温下的二氯甲烷中高效进行，生成相应的二糖。尽管通过原位异头化过程合成α-糖苷的一锅法被认为是困难的，因为糖苷卤化物容易与三甲基硅酸乙酸酯反应，再生出糖苷醋酸酯，作为糖苷供体的起始物。
• Fluorous thiols in oligosaccharide synthesis
  作者：Yuqing Jing、Xuefei Huang

  DOI：10.1016/j.tetlet.2004.04.116

  日期：2004.6

  odorless fluorous thiol is synthesized, which is utilized to prepare highly fluorinated thioglycosyl donors. These thioglycosides showed excellent reactivities in glycosylation reactions. The fluorous chain, stable under esterification, etherification, deacetylation, and glycosylation conditions, allowed facile purification of the thioglycosides by solid-phase extraction through fluorous silica gel

  合成了一种新的几乎无味的氟代硫醇，该硫醇用于制备高度氟化的硫代糖基供体。这些硫糖苷在糖基化反应中显示出极好的反应性。氟链在酯化，醚化，脱乙酰基和糖基化条件下稳定，从而允许通过固相萃取通过氟硅胶轻松纯化硫代糖苷。氟硫醇易于回收。
• A novel intramolecular decarboxylative glycosylation via mixed carbonate
  作者：Takamasa Iimori、Takafumi Shibazaki、Shiro Ikegami

  DOI：10.1016/0040-4039(96)00272-9

  日期：1996.3

  A two-step glycosylation procedure, which involves (1) linking two sugars by using carbonate as a connector, (2) removing carbon dioxide to form a glycosidic bond by the aid of Lewis acid, has been developed. This glycosylation procedure was based on the opposite mode of connection, where a glycosyl acceptor was activated to link sugars.

  已经开发出两步糖基化方法，其涉及（1）通过使用碳酸盐作为连接物来连接两个糖，（2）借助于路易斯酸去除二氧化碳以形成糖苷键。该糖基化过程基于相反的连接方式，其中糖基受体被激活以连接糖。
• Glycosyl Sulfonylcarbamates:  New Glycosyl Donors with Tunable Reactivity
  作者：Ronald J. Hinklin、Laura L. Kiessling

  DOI：10.1021/ja005735i

  日期：2001.4.1

  glycosylation enabled the chemical synthesis of oligosaccharides.1 Since that advance, the differences in regiochemistry and stereochemistry of glycosyl linkages and variations in the stereoelectronic properties of glycosyl donors and acceptors have impelled the search for milder and more selective procedures.2 Successes in this pursuit have expanded the variety of complex, saccharidecontaining natural products

  Koenigs-Knorr 糖基化方法的出现使寡糖的化学合成成为可能。1 自那以来，糖基键的区域化学和立体化学的差异以及糖基供体和受体的立体电子特性的变化推动了对更温和、更多2 这一追求的成功扩大了可通过化学合成获得的复杂的含糖天然产物的种类。然而，给定供体-受体对的选择方法取决于许多变量。一个这样的参数是异头离去基团的性质。从单一中间体产生各种糖基供体的不同合成策略将促进不同糖苷键的构建。寻找这样的捐赠者，我们探索了糖基磺酰基氨基甲酸酯的糖基化反应。我们假设糖基磺酰基氨基甲酸酯可以作为糖基供体，具有独特的特征：这些供体的反应性可以通过合成后修饰进行调节。烯丙基 3 和苯基 4 糖基氨基甲酸酯先前已被证明作为糖基供体。同样，我们设想用亲电子促进剂处理糖基磺酰基氨基甲酸酯会导致 CO2 和磺酰胺的损失，同时产生反应性糖基供体（图 1）。磺酰基氨基甲酸酯基团的一个独特特征是它可以通过 N-烷基
• Glycosyl trichloroacetylcarbamate: a new glycosyl donor for O-glycosylation
  作者：K. Jayakanthan、Yashwant D. Vankar

  DOI：10.1016/j.carres.2005.07.024

  日期：2005.12

  Glycosyl trichloroacetylcarbamates, readily obtained by reacting 1-hydroxy sugars with trichloroacetylisocyanate, have been found as excellent glycosyl donors, and the corresponding O-glycosides are formed in good to excellent yields with a fairly good degree of selectivity. (c) 2005 Elsevier Ltd. All rights reserved.