1-C-benzyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranose | 389121-73-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-C-benzyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranose
• 英文别名: (2S,3R,4S,5R,6R)-2-benzyl-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol
• CAS: 389121-73-7
• 化学式: C₄₁H₄₂O₆
• 分子量: 630.781
• InChiKey: ACJXTJOZMROWDH-WEOXEBIHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  47
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  1-C-benzyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranose 在 三乙基硅烷 、 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 以90%的产率得到(2,3,4,6-Tetra-O-benzyl-β-D-glucopyranosyl)phenylmethane
  参考文献：
  名称：

  A new oxa-Michael reaction and a gold-catalysed cyclisation en route to C-glycosides

  摘要：

  Two new syntheses of benzyl C-glycosides have been developed. The first one involves an unprecedented oxa-Michael cyclisation and the second one relies on an efficient gold-catalysed ring-closure. (c) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.02.022
• 作为产物：
  描述：

  2,3,4,6-四苄基-D-吡喃葡萄糖 在 二甲基亚砜 作用下， 以 乙酸酐 为溶剂， 生成 1-C-benzyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranose
  参考文献：
  名称：

  轻松合成共轭外糖

  摘要：

  探索了两种用于合成各种缀合的外糖的有效方法：（i）通过亲核加糖内酯并随后进行脱水，以及（ii）C-糖苷的硒化并随后去除亚硒氧化物。这些反应以立体选择性方式发生，以仅或主要给出外糖的（Z）-异构体。

  DOI：

  10.1016/s0040-4039(01)01427-7

文献信息

• Stereochemistry in the Synthesis and Reaction of <i>e</i><i>xo</i>-Glycals
  作者：Wen-Bin Yang、Yu-Ying Yang、Yu-Feng Gu、Shwu-Huey Wang、Che-Chien Chang、Chun-Hung Lin

  DOI：10.1021/jo0255227

  日期：2002.5.1

  Two general methods are explored for the stereoselective synthesis of exo-glycals. One method utilizes a nucleophilic addition of fully protected sugar lactones of gluco-, galacto-, and manno-types, followed by the subsequent dehydration, to give the desired exo-glycals with (Z)-configuration. The other method proceeds with selenylation of C-glycosides in a stereoselective manner. The subsequent selenoxide

  探索了两种一般方法来立体选择性合成外糖。一种方法利用亲核加成葡萄糖，半乳糖和甘露糖型的完全保护的糖内酯，随后进行脱水，以得到具有（Z）构型的期望的外糖。另一种方法以立体选择性方式进行C-糖苷的硒化。随后的亚硒酸盐消除也提供了（Z）-外糖。制备的葡萄糖型或甘露型的外糖共轭酯与烯丙醇反应，仅得到α-异头物。
• Synthesis of 1-C-alkyl-α-d-glucopyranosides by Lewis acid- or Brønsted acid-catalyzed O-glycosidation
  作者：Takashi Yamanoi、Yoshiki Oda、Sho Matsuda、Ippo Yamazaki、Kazuhide Matsumura、Kaname Katsuraya、Mikio Watanabe、Toshiyuki Inazu

  DOI：10.1016/j.tet.2006.08.059

  日期：2006.10

  donors to synthesize 1-C-alkyl-d-glucopyranosides were investigated. Using 10 mol % of triphenylmethyl perchlorate efficiently catalyzed the glycosidation of 2,3,4,6-tetra-O-benzyl-1-C-methyl-α-d-glucopyranosyl dimethylphosphinothioate. The glycosidation using the 1-C-alkyl-2,3,4,6-tetra-O-benzyl-α-d-glucopyranosyl acetates smoothly proceeded in the presence of only 5 mol % of scandium(III) trifluoromethanesulfonate

  我们制备了几种1- C-烷基-2,3,4,6-四-O-苄基-α-d-吡喃葡萄糖衍生物，它们的端基均含有甲基，乙基，正丁基和苄基作为烷基职位。研究了路易斯酸或布朗斯台德酸催化的O-糖基化反应，将其用作糖基供体以合成1- C-烷基-d-吡喃葡萄糖苷。使用10mol％的高氯酸三苯甲基酯有效地催化了2,3,4,6-四-O-苄基-1- C-甲基-α-d-吡喃葡萄糖基二甲基硫代磷酸酯的糖基化。使用1- C-烷基-2,3,4,6-四-O的糖基化在仅5mol％的三氟甲磺酸scan（III）的存在下，-苄基-α-d-吡喃葡萄糖基乙酸酯平稳地进行。使用5 mol％的双（三氟甲烷）磺酰亚胺，可显着促进使用1- C-烷基-2,3,4,6-四-O-苄基-α-d-吡喃葡萄糖的脱水-缩合型糖基化作用。这些糖苷化以高收率和高α-立体选择性成功地提供了各种1- C-烷基-α-d-吡喃葡萄糖苷。
• Trimethylsilyl Trifluoromethanesulfonate Catalyzed Nucleophilic Substitution To Give <i>C</i>- and <i>N</i>-Glucopyranosides Derived from <scp>d</scp>-Glucopyranose
  作者：Takashi Yamanoi、Yoshiki Oda

  DOI：10.1055/s-2007-983882

  日期：2007.10

  This paper describes the synthesis of C- and N-glucopyranosides via trimethylsilyl trifluoromethanesulfonate catalyzed nucleophilic substitution of glucopyranosides, derived from d-glucopyranose, with methyl, ethyl, n-butyl, allyl, benzyl, and phenyl groups at the anomeric carbon centers. Generally, the reactions using allyltrimethylsilane, trimethylsilyl azide, trimethylsilyl cyanide, and 1-phenyl-1-(trimethylsiloxy)ethene as the nucleophiles in the presence of 20 mol% trimethylsilyl trifluoromethanesulfonate in acetonitrile­ at -40 °C smoothly proceeded with α-stereoselectivity to afford various C- and N-glucopyranosides in 78-99% yield. Although a decrease in the synthetic yields was observed for some reactions using glucopyranoses with allyl and benzyl groups at the anomeric carbon, the yields could be improved using glucopyranosyl acetates in the presence of 20 mol% trimethylsilyl trifluoro­methanesulfonate in acetonitrile-dichloromethane (1:1) at -78 °C.

  本文描述了通过三甲基硅基三氟甲磺酸盐催化的亲核取代反应合成C-和N-葡萄糖吡喃糖苷，该反应是通过将来自D-葡萄糖吡喃糖的葡萄糖吡喃糖苷与甲基、乙基、正丁基、烯丙基、苄基和苯基等在异头碳中心进行的。通常，在-40°C时，在20摩尔%的三甲基硅基三氟甲磺酸盐存在下，使用烯丙基三甲基硅烷、三甲基硅基叠氮化物、三甲基硅基氰化物和1-苯基-1-(三甲基硅氧基)乙烯作为亲核试剂的反应顺利进行，并表现出α立体选择性，产率在78-99%之间。尽管对于某些使用含有烯丙基和苄基的葡萄糖吡喃糖在异头碳的反应观察到了合成产率的下降，但在-78°C的氯乙烯-二氯甲烷（1:1）混合物中使用葡萄糖吡喃糖醋酸酯并在存在20摩尔%三甲基硅基三氟甲磺酸盐的条件下，产率可以得到改善。
• The Brfnsted Acid-catalyzed O-Glycosidation of 1-C-Alkyl-D-glucopyranose Derivatives
  作者：Takashi Yamanoi、Sho Matsuda、Ippo Yamazaki、Ryo Inoue、Keita Hamasaki、Mikio Watanabe

  DOI：10.3987/com-06-10684

  日期：——

  We found that the O-glycosidation between various kinds of 1-C-alkyl-2,3,4,6-tetra-O-benzyl-D-glucopyanoses and alcohols in the presence of 5 mol % of trifluoromethanesulfonic acid or bis(trifluoromethane)sulfonimide stereoselectively produced the corresponding 1-C-alkyl-alpha-D-glucopyranosides in good yields.
• A new oxa-Michael reaction and a gold-catalysed cyclisation en route to C-glycosides
  作者：Sébastien Redon、Michel Wierzbicki、Joëlle Prunet

  DOI：10.1016/j.tetlet.2013.02.022

  日期：2013.4

  Two new syntheses of benzyl C-glycosides have been developed. The first one involves an unprecedented oxa-Michael cyclisation and the second one relies on an efficient gold-catalysed ring-closure. (c) 2013 Elsevier Ltd. All rights reserved.