2,5,5-trimethyl-2-<2'-<4''-(1(S)-carboxyethyl)-1''(R)-methyl-3''-<(trimethylsilyl)methylene>cyclohex-2''-yl>ethyl>-1,3-dioxane | 116400-02-3

• 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: 2,5,5-trimethyl-2-<2'-<4''-(1(S)-carboxyethyl)-1''(R)-methyl-3''-<(trimethylsilyl)methylene>cyclohex-2''-yl>ethyl>-1,3-dioxane
• 英文别名: 2,5,5-trimethyl-2-(2'-{4''-(1(S)-carboxyethyl)-1''(R)-methyl-3''-[(trimethylsilyl)methylene]cyclohex-2''-yl}ethyl)-1,3-dioxane；(2R)-2-[(1S,2E,3S,4R)-4-methyl-3-[2-(2,5,5-trimethyl-1,3-dioxan-2-yl)ethyl]-2-(trimethylsilylmethylidene)cyclohexyl]propanoic acid
• CAS: 116400-02-3
• 化学式: C₂₃H₄₂O₄Si
• 分子量: 410.67
• InChiKey: GMHXYJUILWFCGK-OOQINTIJSA-N

物化性质

• 沸点：
  481.6±20.0 °C(Predicted)
• 密度：
  0.982±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.74
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,5,5-trimethyl-2-<2'-<4''-(1(S)-carboxyethyl)-1''(R)-methyl-3''-<(trimethylsilyl)methylene>cyclohex-2''-yl>ethyl>-1,3-dioxane 在 氧气 、 草酸 、 silica gel 、 臭氧 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 脱氧青蒿素
  参考文献：
  名称：

  Stereoselective total synthesis of (+)-artemisinin, the antimalarial constituent of Artemisia annua L

  摘要：

  A 10-step stereoselective total synthesis of the antimalarial cadinane sesquiterpene (+)-artemisinin (1) is described. Elaboration of (R)-(+)-pulegone to the known sulfoxide 11 was followed by dianion alkylation and desulfurization to provide the trans-2,3-substituted cyclohexanone 7. Homologation to the cyclohexenecarboxaldehyde 6 was followed by a diastereoselective silyl anion addition to afford the silyl acetate 15. Tandem Claisen ester-enolate rearrangement and dianion alkylation furnished the fully functionalized vinylsilane 18 that underwent abnormal ozonolysis and cyclization to provide the natural product 1.

  DOI：

  10.1021/ja00029a028
• 作为产物：
  描述：

  2,5,5-trimethyl-2-<2'-((1''S)-2''-formyl-6''(R)-methylcyclohex-2''-enyl)ethyl>-1,3-dioxane 在 4-二甲氨基吡啶 、 正丁基锂 、 二乙胺 、 lithium diisopropyl amide 作用下， 反应 16.17h， 生成 2,5,5-trimethyl-2-<2'-<4''-(1(S)-carboxyethyl)-1''(R)-methyl-3''-<(trimethylsilyl)methylene>cyclohex-2''-yl>ethyl>-1,3-dioxane
  参考文献：
  名称：

  Stereoselective total synthesis of (+)-artemisinin, the antimalarial constituent of Artemisia annua L

  摘要：

  A 10-step stereoselective total synthesis of the antimalarial cadinane sesquiterpene (+)-artemisinin (1) is described. Elaboration of (R)-(+)-pulegone to the known sulfoxide 11 was followed by dianion alkylation and desulfurization to provide the trans-2,3-substituted cyclohexanone 7. Homologation to the cyclohexenecarboxaldehyde 6 was followed by a diastereoselective silyl anion addition to afford the silyl acetate 15. Tandem Claisen ester-enolate rearrangement and dianion alkylation furnished the fully functionalized vinylsilane 18 that underwent abnormal ozonolysis and cyclization to provide the natural product 1.

  DOI：

  10.1021/ja00029a028