(1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-11,11-dimethoxy-6-(1-ethoxyethoxy)-3-pivaloyloxytricyclo[6.2.1.0^2,7]undeca-4,9-diene | 255828-83-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-11,11-dimethoxy-6-(1-ethoxyethoxy)-3-pivaloyloxytricyclo[6.2.1.0^2,7]undeca-4,9-diene
• 英文别名: [(1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-6-(1-ethoxyethoxy)-11,11-dimethoxy-3-tricyclo[6.2.1.02,7]undeca-4,9-dienyl] 2,2-dimethylpropanoate
• CAS: 255828-83-2
• 化学式: C₂₂H₃₀Cl₄O₆
• 分子量: 532.289
• InChiKey: BIVPRGJVFSFJCN-LCIJDSNESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-11,11-dimethoxy-6-(1-ethoxyethoxy)-3-pivaloyloxytricyclo[6.2.1.0^2,7]undeca-4,9-diene 在 2,6-二甲基吡啶 、 sodium hydroxide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 67.0h， 生成 (1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-11,11-dimethoxy-3-tert-butyldimethylsilyloxy-6-(1-ethoxyethoxy)tricyclo[6.2.1.0^2,7]undeca-4,9-diene
  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
• 作为产物：
  描述：

  (4S)-4-tert-butyl-3-pivaloyl-1,3-thiazolidine-2-thione 在 4-甲基苯磺酸吡啶 作用下， 以 正庚烷 、 二氯甲烷 为溶剂， 反应 96.75h， 生成 (1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-11,11-dimethoxy-6-(1-ethoxyethoxy)-3-pivaloyloxytricyclo[6.2.1.0^2,7]undeca-4,9-diene
  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