(+/-)5-methylbicyclo<3.2.0>heptan-2-one | 50459-35-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)5-methylbicyclo<3.2.0>heptan-2-one
• 英文别名: 1-methylbicyclo<3.2.0>heptane-4-one；5-methylbicyclo<3.2.0>heptan-2-one；5-Methylbicyclo<3.2.0>heptan-2-on；(1SR,5SR)-5-methylbicyclo[3.2.0]heptan-2-one；cis-(+/-)-5-Methylbicyclo<3.2.0>heptan-2-on；(+/-)5-Methylbicyclo<3.2.0>heptan-2-on；(1R,5R)-5-methylbicyclo[3.2.0]heptan-2-one
• CAS: 50459-35-3
• 化学式: C₈H₁₂O
• 分子量: 124.183
• InChiKey: CENJLQWZLXMSIR-POYBYMJQSA-N

物化性质

• 沸点：
  184.9±8.0 °C(Predicted)
• 密度：
  1.066±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)5-methylbicyclo<3.2.0>heptan-2-one 以 乙醚 为溶剂， 生成 (1R,2S)-2-acetyl-1-methylcyclobutaneacetic acid
  参考文献：
  名称：

  外消旋Grandisol的立体选择性全合成：一种改进的简便方法

  摘要：

  （±）Grandisol是通过实用且方便的方法，以Salomon光双环化为关键步骤，以31％的总收率立体合成的。

  DOI：

  10.1016/s0040-4020(01)82358-9
• 作为产物：
  描述：

  (S)-6-Methyl-1,6-heptadien-3-ol 在 chromium(VI) oxide 、 硫酸 、 三氟甲烷磺酸亚铜(I)苯联合体 (2:1) 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 1.0h， 生成 (+/-)5-methylbicyclo<3.2.0>heptan-2-one
  参考文献：
  名称：

  Stereoselective Intramolecular Copper(I)-Catalyzed [2 + 2]- Photocycloadditions. Enantioselective Synthesis of (+)- and (-)-Grandisol

  摘要：

  This work deals with copper(I)-catalyzed intramolecular [2 + 2]-photocycloadditions of 1,6-diene derivatives. The bridgehead carbons C-l and C-5 of the resulting bicyclo[3.2.0]heptanes are generated stereoselectively by using chiral starting material, chiral catalysts, or chiral auxiliaries. The irradiation of (S)-3 leads to enantiomerically pure 4 and 5 which opens a new synthetic route to enantiomerically pure (+)- and (-)-grandisol 9. The use of chiral copper complexes as catalysts delivers enantiomeric excesses below 5%. The reason for these small excesses is a low reactivity of the chiral copper complexes, as confirmed by CD-spectroscopic measurements. Malic acid or amino carboxylic acid derivatives as chiral auxiliaries yield the bicyclic alcohols 4 and 5 with enantiomeric excesses up to 15%. The employment of a chiral diol as an auxiliary delivers a chiral ketal 36, and the resulting ketone 7 exhibits enantiomeric excesses up to 60%.

  DOI：

  10.1021/jo00127a034

文献信息

• A rearrangement approach to (±)-cerapicol
  作者：Nizar El-Hachach、Matthias Fischbach、Ralf Gerke、Lutz Fitjer

  DOI：10.1016/s0040-4020(99)00258-6

  日期：1999.5

  The synthesis and rearrangement of the cyclobutyl methanol 4 is described. The synthesis has been achieved by addition of the Grignard reagent 16 to the bicyclic ketone 22. Experimental procedures for the preparation of both compounds are given. Upon treatment with trifluoroacetic acid and subsequent reduction, 4 yields the norbornanes 24 and 25 and (±)-cerapicol (8). Some consequences concerning the

  描述了环丁基甲醇4的合成和重排。通过将格氏试剂16添加到双环酮22中来实现合成。给出了制备两种化合物的实验程序。用三氟乙酸处理并随后还原后，得到4降冰片烷24和25和（±）-cerapicol（8）。讨论了有关寻找8的其他潜在前体的一些结果。
• A new asymmetric synthesis of (+)-grandisol via a kinetic resolution
  作者：David P.G. Hamon、Kellie L. Tuck

  DOI：10.1016/s0040-4039(99)01605-6

  日期：1999.10

  A novel approach to the asymmetric synthesis of (+)-grandisol involves the use of catalytic kinetic resolution of a primary allylic alcohol. The allylic alcohol is prepared in 4 steps from simple achiral materials and the resolved alcohol (95%e.e.) is reduced in 2 steps to the corresponding methyl alkene. This alkene is converted to (+)-grandisol (95%e.e.).

  （+）-大丁醇的不对称合成的新方法涉及伯烯丙基醇的催化动力学拆分。由简单的非手性材料分四步制备烯丙醇，然后分两步将拆分的醇（95％ee）还原为相应的甲基烯烃。该烯烃被转化为（+）-大醇（95％ee）。
• Concerning kinetic resolution by the Sharpless asymmetric dihydroxylation reaction
  作者：Hamish S. Christie、David P. G. Hamon、Kellie L. Tuck

  DOI：10.1039/a906423k

  日期：——

  The transition state for the product-determining step in the Sharpless asymmetric dihydroxlation reaction is not product-like, and effective kinetic resolution can occur when one face of a chiral alkene is hindered.

  在 Sharpless 不对称二羟基化反应中，决定产物步骤的过渡态并不像产物，当手性烯烃的一个面受到阻碍时，就会发生有效的动力学解析。
• Synthesis of the both enantiomers of grandisol, the boll weevil pheromone
  作者：K. Mori

  DOI：10.1016/0040-4020(78)88139-3

  日期：1978.1

  Optically active forms of grandisol (2-isopropenyl-1-methylcyclobutane ethanol, 1 and 1') were synthesized from optically active 5-carboxybicyclo[3.2.0]heptan-2-one (2 and its antipode), obtained by resolving the racemate. The optical purities of the synthetic products were determined by the NMR studies using a chiral shift reagent and shown to be 80%. The [α]D values of our synthetic grandisols were

  旋光性形式的大丁醇（2-异丙烯基-1-甲基环丁烷乙醇，1和1 '）是通过拆分外消旋体而获得的旋光性5-羧基双环[3.2.0]庚烷-2-酮（2及其对映体）合成的。合成产物的光学纯度通过使用手性位移试剂的NMR研究确定，显示为80％。我们的合成大单体的[α] D值为±20°（校正后），与马格纳斯的合成（+）-大三角醇（校正后为+ 18.5°）一致，与自然信息素的报道值（+50±10°）不同）。
• Synthesis and solvolysis of derivatives of 7-methyl-7-hydroxynorbornane and the epimeric 7-methyl-7-hydroxynorbornenes
  作者：Paul G. Gassman、John M. Pascone

  DOI：10.1021/ja00804a042

  日期：1973.11