3,5-dimethoxy-2-[(Z)-2-(2,6,6-trimethyl-5-oxocyclohexen-1-yl)ethenyl]benzaldehyde | 153786-89-1

• 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: 3,5-dimethoxy-2-[(Z)-2-(2,6,6-trimethyl-5-oxocyclohexen-1-yl)ethenyl]benzaldehyde
• CAS: 153786-89-1
• 化学式: C₂₀H₂₄O₄
• 分子量: 328.408
• InChiKey: QGAQQQIBCMTWAO-FPLPWBNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  3,5-dimethoxy-2-[(Z)-2-(2,6,6-trimethyl-5-oxocyclohexen-1-yl)ethenyl]benzaldehyde 在 吡啶 、 四氯化钛 、 间氯过氧苯甲酸 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.5h， 生成
  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 manganese(IV) oxide 、 palladium diacetate 、 氢氧化钾 、 双氧水 、 碘 、 对甲苯磺酸 、 三乙胺 、 三苯基膦 、 红铝 、 三氯氧磷 、 原甲酸三甲酯 作用下， 以 吡啶 为溶剂， 生成 3,5-dimethoxy-2-[(Z)-2-(2,6,6-trimethyl-5-oxocyclohexen-1-yl)ethenyl]benzaldehyde
  参考文献：
  名称：

  An AC → ABC approach to taxol involving B-ring closure at C-1–C-2

  摘要：

  The treatment of keto aldehyde 13 with low-valent Ti results in a stereoselective intramolecular pinacol coupling that produces taxane synthesis intermediate 14.

  DOI：

  10.1016/s0040-4039(00)61582-4

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.
• Unusual oxidative transformations of a C-aromatic taxane diene and related structures
  作者：Charles S. Swindell、Madhavi C. Chander

  DOI：10.1016/0040-4039(94)88059-x

  日期：1994.8

  The interaction of 1 and related substances with MCPBA, dimethyldioxirane, VO(acach)(2)-t-BuOOH, and Mo(C0)(6)-t-BuOOH affords products with oxygenated A-rings and/or cleaved B-rings through novel oxidative processes.
• 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.