3-[(Z)-2-[2-(hydroxymethyl)-4,6-dimethoxyphenyl]ethenyl]-2,2,4-trimethylcyclohex-3-en-1-one | 153786-87-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-[(Z)-2-[2-(hydroxymethyl)-4,6-dimethoxyphenyl]ethenyl]-2,2,4-trimethylcyclohex-3-en-1-one
• CAS: 153786-87-9
• 化学式: C₂₀H₂₆O₄
• 分子量: 330.424
• InChiKey: JCRNLKPYELQFEZ-FPLPWBNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  3-[(Z)-2-[2-(hydroxymethyl)-4,6-dimethoxyphenyl]ethenyl]-2,2,4-trimethylcyclohex-3-en-1-one 在 甲基磺酰氯 、 二异丙胺 、 lithium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.5h， 以65%的产率得到3-[(Z)-2-[2-(iodomethyl)-4,6-dimethoxyphenyl]ethenyl]-2,2,4-trimethylcyclohex-3-en-1-one
  参考文献：
  名称：

  Taxane Synthesis through Intramolecular Pinacol Coupling at C-1−C-2. Construction and Oxidative Transformations of a C-Aromatic Taxane Diene

  摘要：

  A ten-linear-step construction of C-aromatic taxane diene 14 from ethyl isopropyl ketone, acryloyl chloride, and commercially available 8 is reported. This sequence concludes with an intramolecular pinacol coupling carried out on 13. 14 is oxidized by m-chloroperbenzoic acid and dimethyldioxirane to give 17 through intermediate epoxide 20 and by VO(acac)(2)-t-BuOOH and Mo(CO)(6)-t-BuOOH to give 13. 17 is converted efficiently into 22 upon treatment with Mo(CO)(6)-t-BuOOH, apparently through an unusual equilibration with isomeric 20, which is converted irreversibly to 22. While these oxidative transformations highlight some of the peculiar reactivity patterns characteristic of taxane-related structures, the formation of 14 through an intramolecular pinacol coupling that joins C-l and C-2 demonstrates the potential of this strategy for stereoselectively delivering advanced taxane synthesis intermediates.

  DOI：

  10.1021/jo951935e
• 作为产物：
  描述：

  3,5-二甲氧基苄醇 在 palladium on barium sulfate 吡啶 、 palladium diacetate 、 氢氧化钾 、 氢气 、 双氧水 、 碘 、 溶剂黄146 、 三乙胺 、 三苯基膦 、 三氯氧磷 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 、 水 、 苯 为溶剂， 25.0 ℃ 、413.69 kPa 条件下， 反应 39.0h， 生成 3-[(Z)-2-[2-(hydroxymethyl)-4,6-dimethoxyphenyl]ethenyl]-2,2,4-trimethylcyclohex-3-en-1-one
  参考文献：
  名称：

  Taxane Synthesis through Intramolecular Pinacol Coupling at C-1−C-2. Construction and Oxidative Transformations of a C-Aromatic Taxane Diene

  摘要：

  A ten-linear-step construction of C-aromatic taxane diene 14 from ethyl isopropyl ketone, acryloyl chloride, and commercially available 8 is reported. This sequence concludes with an intramolecular pinacol coupling carried out on 13. 14 is oxidized by m-chloroperbenzoic acid and dimethyldioxirane to give 17 through intermediate epoxide 20 and by VO(acac)(2)-t-BuOOH and Mo(CO)(6)-t-BuOOH to give 13. 17 is converted efficiently into 22 upon treatment with Mo(CO)(6)-t-BuOOH, apparently through an unusual equilibration with isomeric 20, which is converted irreversibly to 22. While these oxidative transformations highlight some of the peculiar reactivity patterns characteristic of taxane-related structures, the formation of 14 through an intramolecular pinacol coupling that joins C-l and C-2 demonstrates the potential of this strategy for stereoselectively delivering advanced taxane synthesis intermediates.

  DOI：

  10.1021/jo951935e

文献信息

• An AC → ABC approach to taxol involving B-ring closure at C-1–C-2
  作者：Charles S. Swindell、Madhavi C. Chander、Julia M. Heerding、Peter G. Klimko、Leera T. Rahman、J.Venkat Raman、Hemalatha Vencataraman

  DOI：10.1016/s0040-4039(00)61582-4

  日期：1993.10

  The treatment of keto aldehyde 13 with low-valent Ti results in a stereoselective intramolecular pinacol coupling that produces taxane synthesis intermediate 14.
• Taxane Synthesis through Intramolecular Pinacol Coupling at C-1−C-2. Construction and Oxidative Transformations of a C-Aromatic Taxane Diene
  作者：Charles S. Swindell、Madhavi C. Chander、Julia M. Heerding、Peter G. Klimko、Leera T. Rahman、Venkat Raman、Hemalatha Venkataraman

  DOI：10.1021/jo951935e

  日期：1996.1.1

  A ten-linear-step construction of C-aromatic taxane diene 14 from ethyl isopropyl ketone, acryloyl chloride, and commercially available 8 is reported. This sequence concludes with an intramolecular pinacol coupling carried out on 13. 14 is oxidized by m-chloroperbenzoic acid and dimethyldioxirane to give 17 through intermediate epoxide 20 and by VO(acac)(2)-t-BuOOH and Mo(CO)(6)-t-BuOOH to give 13. 17 is converted efficiently into 22 upon treatment with Mo(CO)(6)-t-BuOOH, apparently through an unusual equilibration with isomeric 20, which is converted irreversibly to 22. While these oxidative transformations highlight some of the peculiar reactivity patterns characteristic of taxane-related structures, the formation of 14 through an intramolecular pinacol coupling that joins C-l and C-2 demonstrates the potential of this strategy for stereoselectively delivering advanced taxane synthesis intermediates.