Acetic acid 5-formyl-2,4,4-trimethyl-3-oxo-cyclohex-1-enyl ester | 146385-06-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Acetic acid 5-formyl-2,4,4-trimethyl-3-oxo-cyclohex-1-enyl ester
• 英文别名: (5-formyl-2,4,4-trimethyl-3-oxocyclohexen-1-yl) acetate
• CAS: 146385-06-0
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: GKSSIJQLWVGYLO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.64
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  60.44
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  Acetic acid 5-formyl-2,4,4-trimethyl-3-oxo-cyclohex-1-enyl ester 在 四氢吡咯 、 cerium(III) chloride 、 potassium tert-butylate 、 三乙胺 作用下， 生成 2-{(S)-[(R)-3-(tert-Butyl-dimethyl-silanyloxy)-4,6,6-trimethyl-5-methylene-cyclohex-3-enyl]-trimethylsilanyloxy-methyl}-1-dimethoxymethyl-3-methoxy-benzene
  参考文献：
  名称：

  C-芳族紫杉碱衍生物的合成

  摘要：

  2-位（紫杉烷编号）的含氧取代基对确定内/外环化进入紫杉烷骨架中涉及的 8 元环系统起着关键作用，芳香紫杉碱衍生物由相应的 2α,9β 制备，通过热外向异构化和路易斯酸诱导的 C-9 和 C-10 位点反转，10α-外环化化合物。

  DOI：

  10.1246/cl.1993.133
• 作为产物：
  描述：

  2,2-Dimethyl-5-oxo-3-(tetrahydro-pyran-2-yloxymethyl)-heptanoic acid ethyl ester 在 对甲苯磺酸 草酰氯 、 potassium tert-butylate 、 二甲基亚砜 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 Acetic acid 5-formyl-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