(Z)-(3R,4S,5R,6R)-2-allylidene-3,4,5-tris(benzyloxy)-6-(benzyloxy)methyltetrahydropyran | 389121-75-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Z)-(3R,4S,5R,6R)-2-allylidene-3,4,5-tris(benzyloxy)-6-(benzyloxy)methyltetrahydropyran
• 英文别名: (2R,3R,4S,5R,6Z)-3,4,5-tris(phenylmethoxy)-2-(phenylmethoxymethyl)-6-prop-2-enylideneoxane
• CAS: 389121-75-9
• 化学式: C₃₇H₃₈O₅
• 分子量: 562.706
• InChiKey: UKLTXAVJGOPJJM-KJYUMVBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  42
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  烯丙醇 、 (Z)-(3R,4S,5R,6R)-2-allylidene-3,4,5-tris(benzyloxy)-6-(benzyloxy)methyltetrahydropyran 在 4 A molecular sieve 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以51%的产率得到allyl (5,6,7,9-tetra-O-benzyl-1,2,3-trideoxy)-α-D-gluco-non-1-eno-4-ulopyranose
  参考文献：
  名称：

  Inter- and intramolecular alcohol additions to exo -glycals

  摘要：

  Various exo-glycals were explored for the glycosidic bond formation and synthesis of spiroacetals in a stereoselcctive manner. The former reaction was an intermolecular alcohol addition to give the S new stereogenic center, resulting from the nucleophilic attack from the bottom face of the sugar ring. The latter one was carried Out by the hydroboration of a sugar diene, followed by a Subsequent acid workup. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)01473-9
• 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 、 三氟乙酸酐 作用下， 以 吡啶 、 乙酸酐 为溶剂， 生成 (Z)-(3R,4S,5R,6R)-2-allylidene-3,4,5-tris(benzyloxy)-6-(benzyloxy)methyltetrahydropyran
  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

• 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。
• Facile synthesis of conjugated exo-glycals
  作者：Wen-Bin Yang、Chung-Yi Wu、Che-Chien Chang、Shwu-Huey Wang、Chin-Fen Teo、Chun-Hung Lin

  DOI：10.1016/s0040-4039(01)01427-7

  日期：2001.9

  efficient methods were explored for the synthesis of various conjugated exo-glycals: (i) by nucleophilic addition of sugar lactones with a subsequent dehydration, and (ii) by selenylation of C-glycosides with a subsequent selenoxide elimination. These reactions occurred in a stereoselective manner to give exclusively or predominantly the (Z)-isomers of exo-glycals.

  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。
• Inter- and intramolecular alcohol additions to exo -glycals
  作者：Chuan-Fa Chang、Wen-Bin Yang、Che-Chien Chang、Chun-Hung Lin

  DOI：10.1016/s0040-4039(02)01473-9

  日期：2002.9

  Various exo-glycals were explored for the glycosidic bond formation and synthesis of spiroacetals in a stereoselcctive manner. The former reaction was an intermolecular alcohol addition to give the S new stereogenic center, resulting from the nucleophilic attack from the bottom face of the sugar ring. The latter one was carried Out by the hydroboration of a sugar diene, followed by a Subsequent acid workup. (C) 2002 Elsevier Science Ltd. All rights reserved.