(-)-2-Isopropylapopinene | 923952-37-8

• 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-Isopropylapopinene
• 英文别名: (1R,5S)-6,6-dimethyl-2-propan-2-ylbicyclo[3.1.1]hept-2-ene
• CAS: 923952-37-8
• 化学式: C₁₂H₂₀
• 分子量: 164.291
• InChiKey: HQZUZTRNTHLWOG-ONGXEEELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (-)-2-Isopropylapopinene 在 过氧乙酸 、 碳酸氢钠 、 溶剂黄146 、 zinc dibromide 作用下， 以 甲苯 为溶剂， 反应 2.0h， 生成 (-)-(1S,2R,5S)-2-isopropyl-6,6-dimethylbicyclo[3.1.1]heptan-3-one
  参考文献：
  名称：

  以α-环（=（1 R）-2,2,3-三甲基环戊-3-烯-1-乙醛）作为（+）- β-坏死酚（=（1 S，3 S）-2 ，2,3-三甲基-4-亚甲基环戊烷甲醇）和檀香状醇†

  摘要：

  为了完成我们从α-樟脑醛（=（1 R）-2,2,3-三甲基环戊-3-烯-1-乙醛）类似物衍生的檀香状醇的构效关系（SAR）的全景图，我们进行了异构化将环氧-异丙基-Apopinene（-）- 2d转化为相应的未报告的α- campholenal类似物（+）- 4d（方案 1）。从已知的3-去甲基衍生的α -campholenal（+） - 4a中，我们制备的饱和类似物（+） - 5a中通过氢化，而杂环醛（+） - 5b中获得经由一个拜耳维利格由已知的甲基酮（+）- 6反应。在随后将醇（+）- 9b氧化为酮（+）- 10并进行适当的烷基Grignard反应后，可以将已知的α-樟脑缩醛（-）- 8b进行氧化硼氢化处理，从而获得3,4-二取代的类似物（ +）-脱水和脱保护后的4f，g。（方案 2）。（+）- 4b或其甲基酮（+）- 4h的环氧化，立体选择性地提供了反式-环氧衍生物11a，b，而次要的顺式-立体异构体（+）-

  DOI：

  10.1002/hlca.200690236
• 作为产物：
  描述：

  桃金娘烯醛 在 四氯化碳 、 copper(l) iodide 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 29.0h， 生成 (-)-2-Isopropylapopinene
  参考文献：
  名称：

  Hydroboration. 90. Synthesis of 2-Isobutyl- and 2-Isopropylapopinenes. Rates and Stoichiometry of the Hydroboration of 2-Organylapopinenes with Borane-Methyl Sulfide and Borane-Tetrahydrofuran

  摘要：

  Two higher analogues of Lu-pinene, 2-isobutyl- and 2-isopropylapopinenes, promising chiral auxiliaries for asymmetric hydroboration, were readily synthesized from alpha-pinene in good chemical yield. A quantitative study was made of the rates and stoichiometry of the hydroboration of a number of representative 2-organylapopinenes (2-R-apopinenes) with representative boranes, such as BH3.SMe(2) (BMS) and BH3.THF, in order to develop a convenient procedure for the synthesis of mono- and bis(2-organylapoisopinocampheyl)boranes [2-R-apoisopinylborane (RapBH(2)) and bis(2-R-apoisopinyl)borane (Rap(2)BH), respectively],under investigation as possible improved asymmetric hydroborating reagents. It was evident that the sterically bulkier 2-R-apopinenes such as 2-phenyl- and 2-isopropylapopinenes reacted with boranes at room temperature to form essentially RapBH(2) in greater than or equal to 195 % yield, while a yield of greater than or equal to 90 % was realized in the case of 2-isobutylapopinene; However, alpha-pinene, and 2-ethyl- and 2-n-propylapopinenes smoothly reacted with boranes to form a mixture of RapBH(2) and Rap(2)BH. Under the reaction conditions employed, 2-ethyl-, 2-n-propyl-, 2-isobutyl-, 2-phenyl-, and 2-isopropylapopinenes failed to produce clean Rap(2)BH. The rate of hydroboration decreased significantly with increase in bulk of the organyl group at the 2-position of the apopinene.

  DOI：

  10.1021/jo00087a016

文献信息

• Hydroboration of Terpenes. 11. Convenient Method for Upgrading 2-Organylapopinenes to High Optical Purity by Reaction of 2-Organylapoisopinocampheylboranes with Suitable Dienes Followed by Displacement with Acetaldehyde
  作者：Herbert C. Brown、Ulhas P. Dhokte

  DOI：10.1021/jo00097a065

  日期：1994.9
• Analogues ofα-Campholenal (= (1R)-2,2,3-Trimethylcyclopent-3-ene-1-acetaldehyde) as Building Blocks for (+)-β-Necrodol (= (1S,3S)-2,2,3-Trimethyl-4-methylenecyclopentanemethanol) and Sandalwood-like Alcohols
  作者：Christian Chapuis、Michel Barthe、Carole Cantatore、Christine Saint-Léger、Patrick Wyss

  DOI：10.1002/hlca.200690236

  日期：2006.11

  relationships (SARs) of sandalwood-like alcohols derived from analogues of α-campholenal (= (1R)-2,2,3-trimethylcyclopent-3-ene-1-acetaldehyde), we isomerized the epoxy-isopropyl-apopinene (−)-2d to the corresponding unreported α-campholenal analogue (+)-4d (Scheme 1). Derived from the known 3-demethyl-α-campholenal (+)-4a, we prepared the saturated analogue (+)-5a by hydrogenation, while the heterocyclic aldehyde

  为了完成我们从α-樟脑醛（=（1 R）-2,2,3-三甲基环戊-3-烯-1-乙醛）类似物衍生的檀香状醇的构效关系（SAR）的全景图，我们进行了异构化将环氧-异丙基-Apopinene（-）- 2d转化为相应的未报告的α- campholenal类似物（+）- 4d（方案 1）。从已知的3-去甲基衍生的α -campholenal（+） - 4a中，我们制备的饱和类似物（+） - 5a中通过氢化，而杂环醛（+） - 5b中获得经由一个拜耳维利格由已知的甲基酮（+）- 6反应。在随后将醇（+）- 9b氧化为酮（+）- 10并进行适当的烷基Grignard反应后，可以将已知的α-樟脑缩醛（-）- 8b进行氧化硼氢化处理，从而获得3,4-二取代的类似物（ +）-脱水和脱保护后的4f，g。（方案 2）。（+）- 4b或其甲基酮（+）- 4h的环氧化，立体选择性地提供了反式-环氧衍生物11a，b，而次要的顺式-立体异构体（+）-
• Hydroboration. 90. Synthesis of 2-Isobutyl- and 2-Isopropylapopinenes. Rates and Stoichiometry of the Hydroboration of 2-Organylapopinenes with Borane-Methyl Sulfide and Borane-Tetrahydrofuran
  作者：Herbert C. Brown、Ulhas P. Dhokte

  DOI：10.1021/jo00087a016

  日期：1994.4

  Two higher analogues of Lu-pinene, 2-isobutyl- and 2-isopropylapopinenes, promising chiral auxiliaries for asymmetric hydroboration, were readily synthesized from alpha-pinene in good chemical yield. A quantitative study was made of the rates and stoichiometry of the hydroboration of a number of representative 2-organylapopinenes (2-R-apopinenes) with representative boranes, such as BH3.SMe(2) (BMS) and BH3.THF, in order to develop a convenient procedure for the synthesis of mono- and bis(2-organylapoisopinocampheyl)boranes [2-R-apoisopinylborane (RapBH(2)) and bis(2-R-apoisopinyl)borane (Rap(2)BH), respectively],under investigation as possible improved asymmetric hydroborating reagents. It was evident that the sterically bulkier 2-R-apopinenes such as 2-phenyl- and 2-isopropylapopinenes reacted with boranes at room temperature to form essentially RapBH(2) in greater than or equal to 195 % yield, while a yield of greater than or equal to 90 % was realized in the case of 2-isobutylapopinene; However, alpha-pinene, and 2-ethyl- and 2-n-propylapopinenes smoothly reacted with boranes to form a mixture of RapBH(2) and Rap(2)BH. Under the reaction conditions employed, 2-ethyl-, 2-n-propyl-, 2-isobutyl-, 2-phenyl-, and 2-isopropylapopinenes failed to produce clean Rap(2)BH. The rate of hydroboration decreased significantly with increase in bulk of the organyl group at the 2-position of the apopinene.