2,5,5-trimethyl-2-<2'-(1''(R)-methyl-3''-oxocyclohex-2''-yl)ethyl>-1,3-dioxane | 116499-71-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,5,5-trimethyl-2-<2'-(1''(R)-methyl-3''-oxocyclohex-2''-yl)ethyl>-1,3-dioxane
• 英文别名: (2R,3R)-3-methyl-2-[2-(2,5,5-trimethyl-1,3-dioxan-2-yl)ethyl]cyclohexan-1-one
• CAS: 116499-71-9
• 化学式: C₁₆H₂₈O₃
• 分子量: 268.397
• InChiKey: HBRCWDWNTABTHO-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  长叶薄荷酮 在 六甲基磷酰三胺 、 alkaline H₂O₂ 、 水 、 sodium hydride 、 间氯过氧苯甲酸 、 氢化铝 、 mercury dichloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 31.5h， 生成 2,5,5-trimethyl-2-<2'-(1''(R)-methyl-3''-oxocyclohex-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

文献信息

• The Total synthesis of (+)-artemisinin and (+)-9-desmethyltemesinin
  作者：Mitchell A. Avery、Clive Jennings-White、Wesley K.M. Chong

  DOI：10.1016/s0040-4039(00)96582-1

  日期：1987.1
• Stereoselective total synthesis of (+)-artemisinin, the antimalarial constituent of Artemisia annua L
  作者：Mitchell A. Avery、Wesley K. M. Chong、Clive Jennings-White

  DOI：10.1021/ja00029a028

  日期：1992.1

  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.