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: (1SR,5SR)-5-methylbicyclo[3.2.0]heptan-2-one；5-methylbicyclo[3.2.0]heptan-2-one；(+/-)5-Methylbicyclo[3.2.0]heptan-2-on；Bicyclo[3.2.0]heptan-2-one, 5-methyl-
• CAS: 50459-35-3
• 化学式: C₈H₁₂O
• 分子量: 124.183
• InChiKey: CENJLQWZLXMSIR-UHFFFAOYSA-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 生成 6-methyl-2-oxabicyclo[4.2.0]octan-3-one
  参考文献：
  名称：

  KAKIUCHI K.; TOBE Y.; ODAIRA Y., J. ORG. CHEM., 1980, 45, NO 4, 729-731

  摘要：

  DOI：
• 作为产物：
  描述：

  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) 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醚 、 环己烷 、 水 、 丙酮 为溶剂， 反应 91.5h， 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

• Enantioselective Intermolecular [2+2] Photocycloaddition Reaction of Cyclic Enones and Its Application in a Synthesis of (−)-Grandisol
  作者：Saner Poplata、Thorsten Bach

  DOI：10.1021/jacs.8b01011

  日期：2018.3.7

  The intermolecular [2+2] photocycloaddition of typical cyclic α,β-unsaturated enones, such as 2-cyclohexenone, with olefins was performed in moderate to good yields (42–82%) and with high enantioselectivity (82%–96% ee). An unusual substitution pattern at the chiral oxazaborolidine-AlBr3 Lewis acid complex that promotes the reaction was found to be crucial for the success of the reaction. The method

  典型的环状 α,β-不饱和烯酮（如 2-环己烯酮）与烯烃的分子间 [2+2] 光环加成以中等至良好的产率（42-82%）和高对映选择性（82%-96% ee ）。发现促进反应的手性恶唑硼烷-AlBr3 路易斯酸络合物的不寻常取代模式对反应的成功至关重要。该方法用于对映选择性合成单萜(-)-格兰地醇，以3-甲基-2-环己烯酮为原料，可分六步完成，总产率为13%。
• An Asymmetric Synthesis of (+)-Grandisol, a Constituent of the Aggregation Pheromone of the Cotton Boll Weevil, via a Kinetic Resolution
  作者：David P. G. Hamon、Kellie L. Tuck

  DOI：10.1021/jo000853+

  日期：2000.11.1

  A novel approach to the asymmetric synthesis of (+)-grandisol, (1R, 2S)-isopropenyl-1-methylcyclobutaneethanol, involves the use of catalytic kinetic resolution of a primary allylic alcohol, [(1RS, 5SR)-5-methylbicyclo[3.2.0]hept-2-en-2-yl] methanol. The allylic alcohol is prepared in four steps from simple achiral materials involving the use of a modified Shapiro reaction. The resolved alcohol (95%

  一种新的不对称合成（+）-大醇，（1R，2S）-异丙烯基-1-甲基环丁烷醇的新方法，涉及催化动力学拆分伯烯丙基醇[[（1RS，5SR）-5-甲基双环[ 3.2.0]庚-2-烯-2-基]甲醇。由简单的非手性材料分四个步骤制备烯丙醇，涉及使用改良的Shapiro反应。然后将拆分的醇（95％ee）分两步还原为相应的甲基烯烃，（1S，5R）-2,5-二甲基双环[3.2.0]庚-2-烯。通过改进的文献方法，通过三个步骤将该烯烃转化为（+）-大丁醇（95％ee）。
• KIRMSE, W.;STREU, J., SYNTHESIS, BRD, 1983, N 12, 994-996
  作者：KIRMSE, W.、STREU, J.

  DOI：——

  日期：——
• KIRMSE, W.;SIEGFRIED, R.;STREU, J., J. AMER. CHEM. SOC., 1984, 106, N 8, 2465-2466
  作者：KIRMSE, W.、SIEGFRIED, R.、STREU, J.

  DOI：——

  日期：——
• KIRMSE, W.;STREU, J., CHEM. BER., 1984, 117, N 12, 3490-3496
  作者：KIRMSE, W.、STREU, J.

  DOI：——

  日期：——