(2R,3R,4aR,5S,7R,8R,8aS)-7-(hydroxymethyl)-2,3-dimethoxy-2,3-dimethyl-5-phenylmethoxy-5,7,8,8a-tetrahydro-4aH-pyrano[3,4-b][1,4]dioxin-8-ol | 1326704-65-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,4aR,5S,7R,8R,8aS)-7-(hydroxymethyl)-2,3-dimethoxy-2,3-dimethyl-5-phenylmethoxy-5,7,8,8a-tetrahydro-4aH-pyrano[3,4-b][1,4]dioxin-8-ol
• CAS: 1326704-65-7
• 化学式: C₁₉H₂₈O₈
• 分子量: 384.427
• InChiKey: SXIYCPDFMXIYFL-ZXVGSPHGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  95.8
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2R,3R,4aR,5S,7R,8R,8aS)-7-(hydroxymethyl)-2,3-dimethoxy-2,3-dimethyl-5-phenylmethoxy-5,7,8,8a-tetrahydro-4aH-pyrano[3,4-b][1,4]dioxin-8-ol 在 4-二甲氨基吡啶 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 28.0h， 生成 [(2R,3R,4aR,5S,7R,8R,8aS)-8-(ethoxymethoxy)-2,3-dimethoxy-2,3-dimethyl-5-phenylmethoxy-5,7,8,8a-tetrahydro-4aH-pyrano[3,4-b][1,4]dioxin-7-yl]methoxy-tert-butyl-dimethylsilane
  参考文献：
  名称：

  Carbocyclization of d-glucose: syntheses of gabosine I and streptol

  摘要：

  D-Glucose was differentially protected with a trans-diacetal at C-2,3, an ethoxymethyl ether at C-4, and a tert-butyldimethylsilyl ether at C-6, and then carbocyclized via a key Horner-Wadsworth-Emmons (HWE) olefination to give a versatile synthetic intermediate, enone 13, which was readily transformed into gabosine I and streptol. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.06.028
• 作为产物：
  描述：

  2,3-丁二酮 、 苄基Alpha-D-吡喃葡萄糖苷 、 原甲酸三甲酯 在 甲醇 、 D(+)-10-樟脑磺酸 作用下， 反应 48.0h， 以53%的产率得到(2R,3R,4aR,5S,7R,8R,8aS)-7-(hydroxymethyl)-2,3-dimethoxy-2,3-dimethyl-5-phenylmethoxy-5,7,8,8a-tetrahydro-4aH-pyrano[3,4-b][1,4]dioxin-8-ol
  参考文献：
  名称：

  Carbocyclization of d-glucose: syntheses of gabosine I and streptol

  摘要：

  D-Glucose was differentially protected with a trans-diacetal at C-2,3, an ethoxymethyl ether at C-4, and a tert-butyldimethylsilyl ether at C-6, and then carbocyclized via a key Horner-Wadsworth-Emmons (HWE) olefination to give a versatile synthetic intermediate, enone 13, which was readily transformed into gabosine I and streptol. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.06.028

文献信息

• Photochemistry of α-Diketones in Carbohydrates: Anomalous Norrish Type II Photoelimination and Norrish-Yang Photocyclization Promoted by the Internal Carbonyl Group
  作者：Dimitri Alvarez-Dorta、Elisa I. León、Alan R. Kennedy、Angeles Martín、Inés Pérez-Martín、Concepción Riesco-Fagundo、Ernesto Suárez

  DOI：10.1002/chem.201303843

  日期：2014.2.24

  regioselectivity of the hydrogen atom transfer (HAT) in Norrish type II photochemical processes. We observed that the 1,5‐HAT regioselectivity can be switched between the two potentially abstractable syn‐1,3‐diaxial hydrogens at H6 and H8. Highly unusual photoproducts from Norrish type II photoelimination and Norrish–Yang photocyclization initiated by the excited internal carbonyl group were obtained

  一系列的置于作为1α-丙酮酰系绳4α二酮d -glucopyranose和d，以便确定在上型Norrish氢原子转移（HAT）的区域选择性的推拉和立体电子效应的影响，制备-glucopyranosiduronic酸骨架二，光化学过程。我们观察到1,5-HAT区域选择性可以在两个可能抽象的syn之间进行切换H6和H8处的-1,3-双轴氢。从Norrish II型光消除和由激发的内部羰基引发的Norrish-Yang光环化获得了非常不寻常的光产物，在某些情况下，合成产率很高。通过结晶状态下的光化学实验研究了Norrish II型光消除中的1,5-HAT过渡态。
• Carbocyclization of d-glucose: syntheses of gabosine I and streptol
  作者：Tony K.M. Shing、Y. Chen、Wai-Lung Ng

  DOI：10.1016/j.tet.2011.06.028

  日期：2011.8

  D-Glucose was differentially protected with a trans-diacetal at C-2,3, an ethoxymethyl ether at C-4, and a tert-butyldimethylsilyl ether at C-6, and then carbocyclized via a key Horner-Wadsworth-Emmons (HWE) olefination to give a versatile synthetic intermediate, enone 13, which was readily transformed into gabosine I and streptol. (C) 2011 Elsevier Ltd. All rights reserved.