dl-1,2,3,4-tetrahydronaphthalene-1,4-diol | 3344-42-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: dl-1,2,3,4-tetrahydronaphthalene-1,4-diol
• 英文别名: trans-Tetralin-1,4-diol；(1S,4S)-1,2,3,4-tetrahydronaphthalene-1,4-diol
• CAS: 3344-42-1；19070-56-5；50987-68-3
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: FTCMTZXWNUAYHT-UWVGGRQHSA-N

物化性质

• 熔点：
  137.8-138 °C
• 沸点：
  353.4±30.0 °C(Predicted)
• 密度：
  1.260±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  trans-1,2,3,4-tetrahydronaphthalene-1,4-diol 在 sodium hydroxide 作用下， 以 甲苯 为溶剂， 生成 dl-1,2,3,4-tetrahydronaphthalene-1,4-diol
  参考文献：
  名称：

  Asymmetric Acylation of sec-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center

  摘要：

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.

  DOI：

  10.1021/jo990892p

文献信息

• Asymmetric Acylation of <i>s</i><i>ec</i>-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center
  作者：Shinji Yamada、Hiroko Katsumata

  DOI：10.1021/jo990892p

  日期：1999.12.1

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.