(1R,2R,3s,4S,5S)-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-ol | 142184-47-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (1R,2R,3s,4S,5S)-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-ol
• 英文别名: 2,4-dimethyl-8-oxabicyclo[3.2.1]-6-octen-3-ol
• CAS: 142184-47-2
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: QCPBKNVOPQAYFS-UJNNQKBNSA-N

物化性质

• 熔点：
  42 °C
• 沸点：
  253.3±40.0 °C(Predicted)
• 密度：
  1.068±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.96
• 重原子数：
  11.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1R,2R,3s,4S,5S)-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-ol 在 二异丁基氢化铝 作用下， 以 正己烷 为溶剂， 反应 36.0h， 以77%的产率得到(1S,2R,3R,4S)-2,4-Dimethyl-cyclohept-5-ene-1,3-diol
  参考文献：
  名称：

  Lautens, Mark; Chiu, Pauline; Colucci, John T., Angewandte Chemie, 1993, vol. 105, # 2, p. 267 - 269

  摘要：

  DOI：
• 作为产物：
  描述：

  (1R,2S,4R,5S)-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-one 在 samarium diiodide 、 异丙醇 作用下， 以 四氢呋喃 为溶剂， 以49%的产率得到(1R,2R,3s,4S,5S)-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-ol
  参考文献：
  名称：

  Desymmetrization of meso [3.2.1]oxabicyclic systems using metal-catalysed asymmetric intramolecular C–H insertion

  摘要：

  Diazoketone derivatives of meso 8-oxabicyclo[3.2.1]octen-3-ones were desymmetrized by an intramolecular C-H insertion mediated by chiral copper and dirhodium catalysts to generate oxatricyclic systems with up to 5 contiguous stereogenic centres and 50% ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.10.026

文献信息

• Enantioselective Enzymatic Desymmetrization of Highly Functionalized <i>Meso</i> Tetrahydropyranyl Diols
  作者：Mathieu Candy、Gérard Audran、Hugues Bienaymé、Cyril Bressy、Jean-Marc Pons

  DOI：10.1021/ol902107g

  日期：2009.11.5

  The enantioselective enzymatic desymmetrization of several highly substituted meso-tetrahydropyranyl diols is described. This transformation leads to valuable building blocks containing up to five stereogenic centers, which are revealed in a single step with both high yields and excellent enantiomeric excesses. Moreover, it was shown that this kind of building blocks could provide an easy access to

  描述了几种高度取代的内消旋-四氢吡喃基二醇的对映选择性酶促不对称化。这种转化导致了有价值的结构单元，其中包含多达五个立体异构中心，这些一步一步即可揭示，同时具有高收率和出色的对映异构体过量。而且，已经表明，这种结构单元可以容易地获得高度官能化的立体四链体的两种对映异构体。
• The effect of remote oxygens on the ring-opening reactions of oxabicyclic compounds with organolithium reagents. Synthesis of the C21–C27 segment of rifamycin S
  作者：Mark Lautens、Randolph K. Belter

  DOI：10.1016/s0040-4039(00)79040-x

  日期：1992.5

  The reactivity of several related oxabicyclo[3.2.1]octenes toward ring-opening was found to depend on the stereochemistry of a remote hydroxyl group. It was also found that attenuation of the reactivity occurred upon protection of the remote alcohol.

  发现一些相关的氧杂双环[3.2.1]辛烯对开环的反应性取决于远程羟基的立体化学。还发现在保护远端的醇时反应活性减弱。
• Competing kinetic pathways in the bromine addition to allylic ethers in 1,2-dichloroethane: Opposite temperature effects
  作者：Alessandro Cecchi、Giuditta Bartalucci、Cinzia Chiappe、Roberto Bianchini

  DOI：10.1002/kin.20217

  日期：2007.4

  of the electrophilic bromination of three allylic ethers in a nonprotic solvent, 1,2-dichloroethane, has been investigated. Two of them followed a prevalent second-order pathway, while the third one exhibited a classical, clean third order. The second-order pathway in the first two olefins is attributed to electrophilic assistance of the ethereal oxygen to the attacking bromine molecule. In the molecular

  研究了三种烯丙基醚在非质子溶剂 1,2-二氯乙烷中的亲电溴化动力学。其中两个遵循流行的二阶途径，而第三个则表现出经典、干净的三阶。前两种烯烃中的二级途径归因于醚氧对攻击性溴分子的亲电辅助。在 2,4-cis-dimethyl-8-oxabicyclo[3.2.1]-6-octen-3-cis-ol 的分子溴化中，发现两种不同的动力学途径具有相反的温度依赖性。与三级分布中的溴-溴化物相比，溴-溴化物离子中间体的稳定性较差，这解释了二级反应的放热过程。© 2007 Wiley Periodicals, Inc. 39: 197–203, 2007
• Chelation-Controlled Reduction of α-Methylated 8-Oxabicyclo[3.2.1]oct-6-en-3-ones with Samarium Diiodide. Diastereoselective Preparation of Secondary Alcohols
  作者：Jens Treu、H. M. R. Hoffmann

  DOI：10.1021/jo970450i

  日期：1997.7.1

  The title reduction has been effected with high stereocontrol using samarium diiodide in the presence of a proton source. It is concluded that chelation of samarium by the ether oxygen of the substrate directs and facilitates the reduction to equatorial alcohol.