(E)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyliden-α-D-glucofuranose | 911660-25-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyliden-α-D-glucofuranose
• 英文别名: 3-benzyloxyimino-1,2-O-isopropylidene-α-D-ribo-hexofuranose；(1R)-1-[(3aR,5S,6E,6aR)-2,2-dimethyl-6-phenylmethoxyimino-3a,6a-dihydrofuro[2,3-d][1,3]dioxol-5-yl]ethane-1,2-diol
• CAS: 911660-25-8
• 化学式: C₁₆H₂₁NO₆
• 分子量: 323.346
• InChiKey: BITDDTUKGIKUBY-GDRMRZJTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  89.7
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (E)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyliden-α-D-glucofuranose 、 (S)-(+)-alpha-甲氧基苯乙酸 在 4-二甲氨基吡啶 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (E)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyliden-α-D-glucofuranose bis-(S)-α-methoxyphenylacetic acid ester
  参考文献：
  名称：

  通过1H NMR光谱预测伯和仲1,2-二醇的绝对立体化学：原理和应用。

  摘要：

  由伯和仲（手性）羟基形成的1,2-二醇的绝对构型可以通过比较相应的（R）-和双-（S）-MPA酯的1H NMR光谱推导得出（MPA =甲氧基苯基乙酸）。该方法涉及使用与仲（手性）碳相连的取代基L1 / L2的化学位移和与手性中心（C alpha-H）相连的氢原子的化学位移作为诊断信号。理论（AM1，HF和B3 LYP计算）和实验数据（动态和低温NMR光谱，氘代衍生物研究，恒定耦合分析，圆二色性（CD）光谱以及使用许多已知绝对二醇的NMR研究）构型）证明为那些信号获得的delta delta（RS）的符号与二醇的绝对构型相关。

  DOI：

  10.1002/chem.200500181
• 作为产物：
  描述：

  1,2:5,6-二-o-异亚丙基-alpha-d-ribo-3-己呋喃核糖 在 Dowex 50W-XB resin 、 potassium acetate 作用下， 以 甲醇 、 水 为溶剂， 反应 24.0h， 生成 (E)-3-benzyloxyimine-3-deoxy-1,2-O-isopropyliden-α-D-glucofuranose
  参考文献：
  名称：

  Formation of Five- and Six-Membered Carbocycles with Nitrogenated Tetrasubstituted Carbons by Radical Addition-Carbocyclization of Alkynyl Ketoxime Ethers

  摘要：

  C3-Ketoxime ethers bearing alkynes with terminal delta-yne or internal gamma-yne functions were prepared in five or six steps and similar to 20% overall yield from commercial glucofuranose derivatives. Their thiyl-, stannyl-, or carbon radical-promoted addition-carbocyclization gave five- or six-membered carbocycles nitrogenated at one of the bridgehead positions. For internal gamma-yne ethers the tandem process was strongly dependent on both the alkyne substituent and the radical-promoting species and could be directed toward either the five- or the six-membered carbocycle. These results are presented and discussed in the context of studies working toward (-)-tetrodotoxin.

  DOI：

  10.1021/jo060883y

文献信息

• The Prediction of the Absolute Stereochemistry of Primary and Secondary 1,2-Diols by1H NMR Spectroscopy: Principles and Applications
  作者：Félix Freire、José M. Seco、Emilio Quiñoá、Ricardo Riguera

  DOI：10.1002/chem.200500181

  日期：2005.9.19

  absolute configuration of 1,2-diols formed by a primary and a secondary (chiral) hydroxyl group can be deduced by comparison of the 1H NMR spectra of the corresponding (R)- and bis-(S)-MPA esters (MPA = methoxyphenylacetic acid). This method involves the use of the chemical shifts of substituents L1/L2 attached to the secondary (chiral) carbon, and of the hydrogen atom linked to the chiral center (C

  由伯和仲（手性）羟基形成的1,2-二醇的绝对构型可以通过比较相应的（R）-和双-（S）-MPA酯的1H NMR光谱推导得出（MPA =甲氧基苯基乙酸）。该方法涉及使用与仲（手性）碳相连的取代基L1 / L2的化学位移和与手性中心（C alpha-H）相连的氢原子的化学位移作为诊断信号。理论（AM1，HF和B3 LYP计算）和实验数据（动态和低温NMR光谱，氘代衍生物研究，恒定耦合分析，圆二色性（CD）光谱以及使用许多已知绝对二醇的NMR研究）构型）证明为那些信号获得的delta delta（RS）的符号与二醇的绝对构型相关。
• Formation of Five- and Six-Membered Carbocycles with Nitrogenated Tetrasubstituted Carbons by Radical Addition-Carbocyclization of Alkynyl Ketoxime Ethers
  作者：Marta Fernández-González、Ricardo Alonso

  DOI：10.1021/jo060883y

  日期：2006.9.1

  C3-Ketoxime ethers bearing alkynes with terminal delta-yne or internal gamma-yne functions were prepared in five or six steps and similar to 20% overall yield from commercial glucofuranose derivatives. Their thiyl-, stannyl-, or carbon radical-promoted addition-carbocyclization gave five- or six-membered carbocycles nitrogenated at one of the bridgehead positions. For internal gamma-yne ethers the tandem process was strongly dependent on both the alkyne substituent and the radical-promoting species and could be directed toward either the five- or the six-membered carbocycle. These results are presented and discussed in the context of studies working toward (-)-tetrodotoxin.