Acetic acid 2,4,4-trimethyl-3-oxo-5-(tetrahydro-pyran-2-yloxymethyl)-cyclohex-1-enyl ester | 157635-53-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Acetic acid 2,4,4-trimethyl-3-oxo-5-(tetrahydro-pyran-2-yloxymethyl)-cyclohex-1-enyl ester
• CAS: 157635-53-5
• 化学式: C₁₇H₂₆O₅
• 分子量: 310.39
• InChiKey: KUANILOWFXNMGA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.98
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  Acetic acid 2,4,4-trimethyl-3-oxo-5-(tetrahydro-pyran-2-yloxymethyl)-cyclohex-1-enyl ester 在 对甲苯磺酸 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 甲醇 为溶剂， 反应 3.0h， 生成 Acetic acid (S)-5-[(R)-(2-dimethoxymethyl-6-methoxy-phenyl)-hydroxy-methyl]-2,4,4-trimethyl-3-oxo-cyclohex-1-enyl ester
  参考文献：
  名称：

  An Efficient Approach toward Taxane Analogs: Atrop- and Diastereoselective Eight-Membered B Ring Cyclizations for Synthesis of Aromatic C-Ring Taxinine Derivatives

  摘要：

  We have developed efficient methods for construction of the C-2 oxygenated aromatic C-ring taxane skeleton based on an eight-membered ring cyclization involving a Lewis acid-mediated intramolecular coupling reaction of the dienol silyl ether at C-10 and the acetal at C-9. The C-2 stereogenic center strongly influences the conformation of the forming eight-membered ring during the cyclization reaction. 1 beta,2 alpha-Siloxy derivative 13b gives exo isomer 15 as the major product, and 1 beta,2 beta-siloxy derivative 13a exclusively yields endo isomer 14. Both of these cyclization products, which had undesired stereochemistry, were converted to stereochemically refined aromatic C-ring taxinine analogs by multistep transformations. The chelation-controlled, eight-membered ring cyclization of 1 beta,2 alpha-hydroxy derivative 31 was found to give exclusively the desired 1 beta,2 alpha,9 alpha,10 beta-endo isomer 16 in good yield. This remarkably stereoselective cyclization, when combined with stereocontrolled AC ring coupling reactions, should provide an efficient, convergent route toward various taxane derivatives. The aromatic C-ring taxinine analogs could be converted to natural taxinine by further transformation of the aromatic C-ring.

  DOI：

  10.1021/jo00090a039
• 作为产物：
  描述：

  (Z)-6-(Tetrahydro-pyran-2-yloxy)-hex-4-en-3-ol 在 草酰氯 、 potassium tert-butylate 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 6.25h， 生成 Acetic acid 2,4,4-trimethyl-3-oxo-5-(tetrahydro-pyran-2-yloxymethyl)-cyclohex-1-enyl ester
  参考文献：
  名称：

  An Efficient Approach toward Taxane Analogs: Atrop- and Diastereoselective Eight-Membered B Ring Cyclizations for Synthesis of Aromatic C-Ring Taxinine Derivatives

  摘要：

  We have developed efficient methods for construction of the C-2 oxygenated aromatic C-ring taxane skeleton based on an eight-membered ring cyclization involving a Lewis acid-mediated intramolecular coupling reaction of the dienol silyl ether at C-10 and the acetal at C-9. The C-2 stereogenic center strongly influences the conformation of the forming eight-membered ring during the cyclization reaction. 1 beta,2 alpha-Siloxy derivative 13b gives exo isomer 15 as the major product, and 1 beta,2 beta-siloxy derivative 13a exclusively yields endo isomer 14. Both of these cyclization products, which had undesired stereochemistry, were converted to stereochemically refined aromatic C-ring taxinine analogs by multistep transformations. The chelation-controlled, eight-membered ring cyclization of 1 beta,2 alpha-hydroxy derivative 31 was found to give exclusively the desired 1 beta,2 alpha,9 alpha,10 beta-endo isomer 16 in good yield. This remarkably stereoselective cyclization, when combined with stereocontrolled AC ring coupling reactions, should provide an efficient, convergent route toward various taxane derivatives. The aromatic C-ring taxinine analogs could be converted to natural taxinine by further transformation of the aromatic C-ring.

  DOI：

  10.1021/jo00090a039