(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 | 215095-43-5

• 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-3-pivaloyloxytricyclo[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-hydroxy-11,11-dimethoxy-3-tricyclo[6.2.1.02,7]undeca-4,9-dienyl] 2,2-dimethylpropanoate
• CAS: 215095-43-5
• 化学式: C₁₈H₂₂Cl₄O₅
• 分子量: 460.182
• InChiKey: INUNNUYICZTGNI-ZSHZHJNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

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-3-pivaloyloxytricyclo[6.2.1.0^2,7]undeca-4,9-dien-6-ol 在 pyridinium chlorochromate 作用下， 生成 2,2-Dimethyl-propionic acid (1R,4S,4aS,5R,8aR)-1,2,3,4-tetrachloro-9,9-dimethoxy-8-oxo-1,4,4a,5,8,8a-hexahydro-1,4-methano-naphthalen-5-yl ester
  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：

  2,2-Dimethyl-thiopropionic acid S-((S)-4-tert-butyl-4,5-dihydro-thiazol-2-yl) ester 以 正庚烷 为溶剂， 反应 96.0h， 生成 (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
  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

• Desymmetrization of meso-Diols by Acylation with Axially Chiral Twisted Amides and Its Mechanistic Studies
  作者：Shinji Yamada、Hiroko Katsumata

  DOI：10.1246/cl.1998.995

  日期：1998.10

  Desymmetrization of meso-1,2-, -1,3-, and -1,4-diols was performed by acylation with chiral twisted amides.1 The conformation of the twisted amides was studied by optimization of the PM3 method in order to elucidate the reaction mechanism. The directionality of the amide bond rotation was considered to be significantly responsible for the stereoselectivity.

  通过手性扭曲酰胺的酰化作用，实现了中-1,2-、-1,3-和-1,4-二醇的不对称化。1 为了阐明反应机理，通过优化PM3方法研究了扭曲酰胺的构象。酰胺键旋转的方向性被认为是立体选择性的重要原因。
• 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.