(1R,2R,3S,6R,7S,8S)-1,8,9,10-tetrachloro-11,11-dimethoxy-3-(1-ethoxyethoxy)tricyclo[6.2.1.0^2,7]undeca-4,9-dien-6-ol | 255828-84-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,2R,3S,6R,7S,8S)-1,8,9,10-tetrachloro-11,11-dimethoxy-3-(1-ethoxyethoxy)tricyclo[6.2.1.0^2,7]undeca-4,9-dien-6-ol
• 英文别名: (1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-6-(1-ethoxyethoxy)-11,11-dimethoxytricyclo[6.2.1.02,7]undeca-4,9-dien-3-ol
• CAS: 255828-84-3
• 化学式: C₁₇H₂₂Cl₄O₅
• 分子量: 448.171
• InChiKey: YUTDJDVZMBDYLP-QIGKRGSCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1R,2R,3S,6R,7S,8S)-1,8,9,10-tetrachloro-11,11-dimethoxy-3-(1-ethoxyethoxy)tricyclo[6.2.1.0^2,7]undeca-4,9-dien-6-ol 在 2,6-二甲基吡啶 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 (1S,4R,4aR,5S,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,5,8,8a-hexahydro-1,4-methano-naphthalen-5-ol
  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：

  (1S,2S,3R,6S,7R,8R)-1,8,9,10-tetrachloro-11,11-dimethoxy-3-pivaloyloxytricyclo[6.2.1.0^2,7]undeca-4,9-dien-6-ol 在 sodium hydroxide 、 4-甲基苯磺酸吡啶 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 65.25h， 生成 (1R,2R,3S,6R,7S,8S)-1,8,9,10-tetrachloro-11,11-dimethoxy-3-(1-ethoxyethoxy)tricyclo[6.2.1.0^2,7]undeca-4,9-dien-6-ol
  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.