methyl (E,2S,6R,8S,9S)-9-[tert-butyl(dimethyl)silyl]oxy-2,4,6,8-tetramethyl-10-methylidene-7-oxododec-4-enoate | 132950-79-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl (E,2S,6R,8S,9S)-9-[tert-butyl(dimethyl)silyl]oxy-2,4,6,8-tetramethyl-10-methylidene-7-oxododec-4-enoate
• CAS: 132950-79-9；139343-71-8；139343-77-4
• 化学式: C₂₄H₄₄O₄Si
• 分子量: 424.696
• InChiKey: LLABXBZJWPPWBQ-KEYUBADCSA-N

物化性质

• 沸点：
  456.9±45.0 °C(Predicted)
• 密度：
  0.928±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.33
• 重原子数：
  29
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (E,2S,6R,8S,9S)-9-[tert-butyl(dimethyl)silyl]oxy-2,4,6,8-tetramethyl-10-methylidene-7-oxododec-4-enoate 在 lithium hydroxide 、 双氧水 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 20.33h， 生成 (E,2S,3S,4S,8R,10S,11S)-11-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-2,4,6,8,10-pentamethyl-12-methylidene-9-oxotetradec-6-enoic acid
  参考文献：
  名称：

  Total synthesis of the esterase inhibitor (±)-ebelactone a using an aldol-claisen strategy

  摘要：

  The beta-lactone (+/-)-ebelactone A has been prepared in 12 steps from diethylketone (9% overall yield) using a series of three boron enolate aldol reactions coupled with the Ireland ester enolate Claisen rearrangement, 10 --> 11.

  DOI：

  10.1016/s0040-4039(00)88532-9
• 作为产物：
  描述：

  2-乙基丙烯醛 在 2,6-二甲基吡啶 、 盐酸 、 4-二甲氨基吡啶 、 三甲基氯硅烷 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 methyl (E,2S,6R,8S,9S)-9-[tert-butyl(dimethyl)silyl]oxy-2,4,6,8-tetramethyl-10-methylidene-7-oxododec-4-enoate
  参考文献：
  名称：

  Total synthesis of the esterase inhibitor (±)-ebelactone a using an aldol-claisen strategy

  摘要：

  The beta-lactone (+/-)-ebelactone A has been prepared in 12 steps from diethylketone (9% overall yield) using a series of three boron enolate aldol reactions coupled with the Ireland ester enolate Claisen rearrangement, 10 --> 11.

  DOI：

  10.1016/s0040-4039(00)88532-9

文献信息

• Total Synthesis of (-)-Ebelactone A and B
  作者：Ian Paterson、Alison N. Hulme

  DOI：10.1021/jo00116a010

  日期：1995.6

  The beta-lactone enzyme inhibitors (-)-ebelactone A (1) and (-)-ebelactone B (2) have been prepared in 12 steps from diethyl ketone (4 and 3% overall yield, respectively). The synthetic strategy adopted for the ebelactones demonstrates the use of reagent- and substrate-derived stereocontrol and requires the minimal use of protecting groups. The stereocenters at C-2, C-3, C-8, C-10, and C-11 were constructed using boron aldol methodology. An asymmetric syn, aldol addition of diethyl ketone to 2-ethyl/acrolein gave adduct 8 in 86% ee, followed by a diastereoselective syn aldol reaction to give 11. Subsequently, an Ireland-Claisen rearrangement was used to relay 1,2-syn into 1,5-syn relative stereochemistry, as in 12 --> 14. In the anti aldol construction of the C-2-C-3 bond, the use of either a propionate or butyrate thioester enolate allowed for a divergent approach from aldehyde 17 to both (-)-ebelactone A and B. Several novel analogues of ebelactone A and B were also prepared with inverted stereochemistry at C-2, C-3, or C-12.