(1R,2S,5R)-(-)-2,5-dimethylbicyclo<3.2.0>heptan-endo-2-ol | 132957-49-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,2S,5R)-(-)-2,5-dimethylbicyclo<3.2.0>heptan-endo-2-ol
• 英文别名: (1R,2S,5R)-2,5-Dimethylbicyclo<3.2.0>heptan-2-ol；(1R,2S,5R)-2,5-dimethylbicyclo[3.2.0]heptan-2-ol
• CAS: 132957-49-4
• 化学式: C₉H₁₆O
• 分子量: 140.225
• InChiKey: OESOHHQESAUIIR-HLTSFMKQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R,2S,5R)-(-)-2,5-dimethylbicyclo<3.2.0>heptan-endo-2-ol 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 生成
  参考文献：
  名称：

  Resolution and EPC synthesis of both enantiomers of 2,5-Dimethylbicyclo[3.2.0]heptan-endo-2-ol, Key Intermediate in the Synthesis of Grandisol.

  摘要：

  The pure enantiomers of 2,5-dimethylbicyclo[3.2.0]heptan-endo-2-ol, key intermediate in the synthesis of grandisol, have been conveniently prepared by optical resolution with (2S)-(-)-and (2R)-(+)-1-(4-toluenesulphonyl)pyrrolidine-2carboxylic acid chloride (NTP-Cl) as resolving agents, and by an EPC synthesis employing commercially available (3R)-(-)-and (3S)-(+)-linalool as chiral sources.

  DOI：

  10.1016/s0957-4166(00)80532-7
• 作为产物：
  描述：

  在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以91%的产率得到(1R,2S,5R)-(-)-2,5-dimethylbicyclo<3.2.0>heptan-endo-2-ol
  参考文献：
  名称：

  Resolution, specific rotation and absolute configuration o f 2,6,6-trimethylbicyclo[3.2.0]heptan-endo-2-ol and of 2,5-dimethylbicyclo[3.2.0]heptan-endo-2-ol, key intermediate in the synthesis of grandisol.

  摘要：

  DOI：

  10.1016/s0957-4166(00)82388-5

文献信息

• A new practical synthesis of (+)-grandisol from (+)-citronellol using an intramolecular carbenoid cyclization
  作者：Hugo J. Monteiro、Julio Zukerman-Schpector

  DOI：10.1016/s0040-4020(96)00175-5

  日期：1996.3

  A new practical 10 step synthesis of (1S,2R)-2-acetyl-1-methylcyclobutaneacetic acid 15 is reported, which has as a key step a rhodium catalyzed intramolecular carbenoid cyclization of the α-diazo-β-ketosulfone 5, readily available from (+)-citronellol 2. Since 15 has already been converted into (+)-grandisol 1, the major pheromone of the cotton boll-weevil Anthonomus grandis, the described preparation

  的一种新的实用的10步合成（1S，2R）-2-乙酰基-1- methylcyclobutaneacetic酸15被报告，其具有作为一个关键步骤铑催化的分子内卡宾的α重氮基β酮砜的环化5，容易获得的来自（+）-香茅醇2。由于15已经被转化为（+）-grandisol 1，即棉铃象鼻虫Anthonomus grandis的主要信息素，因此所描述的制备方法构成了光学活性信息素的新形式合成。
• Stereoselective Intramolecular Copper(I)-Catalyzed [2 + 2]- Photocycloadditions. Enantioselective Synthesis of (+)- and (-)-Grandisol
  作者：Klaus Langer、Jochen Mattay

  DOI：10.1021/jo00127a034

  日期：1995.11

  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%.