(+)-trans,trans-2,8-dimethyl-1,7-dioxaspiro<5.5>undecane | 90760-46-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-trans,trans-2,8-dimethyl-1,7-dioxaspiro<5.5>undecane
• 英文别名: (-)-trans,trans-2,8-dimethyl-1,7-dioxaspiro<5.5>undecane；trans,trans-2,8-dimethyl-1,7-dioxaspiro<5.5>undecane；(E,E)-2,8-dimethyl-1,7-dioxaspiro<5.5>undecane；2,8-Dimethyl-1,7-dioxaspiro<5.5>undecane；(+/-)-(E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane；2,8-dimethyl-1,7-dioxaspiro[5.5]undecane
• CAS: 90760-46-6
• 化学式: C₁₁H₂₀O₂
• 分子量: 184.279
• InChiKey: AHOKGTBIWXGZNE-GARJFASQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (+)-trans,trans-2,8-dimethyl-1,7-dioxaspiro<5.5>undecane 在 potassium tert-butylate 、 溴 、 calcium carbonate 作用下， 以 四氢呋喃 、 四氯化碳 、 二甲基亚砜 为溶剂， 生成 2,8-Dimethyl-1,7-dioxaspiro<5.5>undecan-4-ol
  参考文献：
  名称：

  .alpha.-Bromo spiroketals: stereochemistry and elimination reactions

  摘要：

  The simple spiroketals, 1,6-dioxaspiro[4.4]nonane (2), 1,6-dioxaspiro[4.5]decane (5), 1,7-dioxaspiro[5.5]undecane (6), and (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (7), have been brominated by bromine in carbon tetrachloride/calcium carbonate or acetic acid, and a number of mono-, di-, and tribromo derivatives have been characterized. The relative stereochemistries have been established by correlated H-1 and C-13 NMR spectroscopy and X-ray crystal structure determinations. Dehydrobromination with potassium tert-butoxide in either dimethyl sulfoxide or tetrahydrofuran is facile for the axial monobromides, although both axial and equatorial bromides derived from 1,6-dioxaspiro[4.5]decane (5) and 1,7-dioxaspiro[5.5]undecane (6) dehydrobrominate to provide 1,6-dioxaspiro[4.5]dec-9-ene (35) and 1,7-dioxaspiro[5.5]undec-4-ene (26), respectively. Hydration of these readily acquired alkenes furnishes the corresponding 9- and 4-ols, respectively, with the latter being components of the rectal glandular secretion of Bactrocera oleae (olive fly), Bactrocera cacuminatus, and Bactrocera distincta. These studies indicate that alpha-bromination of suitable spiroketals may be a viable later step in the synthesis of alpha-bromine-containing spiroketal metabolites such as obtusin and neoobtusin.

  DOI：

  10.1021/jo00061a025
• 作为产物：
  描述：

  在 Amberlite IR 120 、 potassium diisopropylamide 、 magnesium sulfate 作用下， 以 四氢呋喃 为溶剂， 反应 49.5h， 生成 (+)-trans,trans-2,8-dimethyl-1,7-dioxaspiro<5.5>undecane
  参考文献：
  名称：

  Synthesis of Spiroacetal Pheromones via Metalated Hydrazones

  摘要：

  通过合适的亲电试剂与金属化丙酮二甲基脲的α,α′-烷基化反应，随后进行酸催化的断裂和环化闭合，描述了简单烷基取代螺缩醛的合成方法。

  DOI：

  10.1055/s-1990-27080

文献信息

• Cyclization of Hydroxyenol Ethers into Spiroacetals. Evidence for the position of the transition state and its implication on the stereoelectronic effects in acetal formation
  作者：Normand Pothier、Solo Goldstein、Pierre Deslongchamps

  DOI：10.1002/hlca.19920750217

  日期：1992.3.18

  controlled cyclizations of the same four hydroxyenol ethers produced, along with the more stable spiroacetals mentioned above, the less stable spiroacetals 23, 25, and 28. These results show that the kinetically controlled cyclization takes place via an early transition state which produces a mixture of the less stable and the more stable isomers. These results are explained by an early transition state

  据报道，在热力学和动力学控制的条件下，羟基烯醇醚18-21具有酸催化的环化作用。18、19和21的热力学控制环化仅产生更稳定的相应螺缩醛22和27。热力学控制的化合物20的环化反应产生了不可模仿的螺缩醛24和26的1：1混合物。另一方面，与上述提到的更稳定的螺缩醛一起生产的相同的四种羟基烯醇醚的动力学控制环化反应，生成的不稳定的螺缩醛23、25和28也更不稳定。。这些结果表明，动力学控制的环化是通过早期过渡态发生的，该过渡态产生了较不稳定和较稳定的异构体的混合物。这些结果由遵循立体电子控制原理的早期过渡态解释，同时遵循反周平面孤对假设（π系统中亲核分子的Bürgi - Dunitz攻角）。
• Spiroacetals from dienones and hydroxyenones by mercury(II) cyclisation
  作者：William Kitching、Judith A. Lewis、Mary T. Fletcher、James J. De Voss、Richard A. I. Drew、Christopher J. Moore

  DOI：10.1039/c39860000855

  日期：——

  Dienones and hydroxyenones are converted efficiently into spiroacetals by hydroxymercuration–cyclisation followed by either reductive or oxidative removal of mercury.

  通过羟基汞化-环化，然后还原或氧化去除汞，将二烯酮和羟烯酮有效地转化为螺缩醛。
• Chemistry of fruit flies. Composition of the rectal gland secretion of (male) Dacus cucumis (cucumber fly) and Dacus halfordiae. Characterization of (Z,Z)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane
  作者：William Kitching、Judith A. Lewis、Michael V. Perkins、Richard Drew、Christopher J. Moore、Volker Schurig、Wilfried A. Koenig、Wittko Francke

  DOI：10.1021/jo00277a028

  日期：1989.8
• Alkynyltrifluoroborates as Versatile Tools in Organic Synthesis:  A New Route to Spiroketals
  作者：Jan Doubský、Ludvík Streinz、David Šaman、Jiří Zedník、Bohumír Koutek

  DOI：10.1021/ol047987k

  日期：2004.12.1

  A simple and efficient two-step approach to spiroketals is described. Key steps include the preparation of functionalized hydroxyl alpha-alkynones by ring-opening reactions of lactones with lithium alkynyltrifluoroborates followed by a palladium-catalyzed hydrogenation/spirocyclization of the prespiroketal intermediate.
• A convenient access to thermodynamically nonstabilised spiroketal isomers: the first synthesis of (Z)-7-methyl-1,6-dioxaspiro[4.5]decane
  作者：Jan Doubský、David Šaman、Jiří Zedník、Soňa Vašíčková、Bohumír Koutek

  DOI：10.1016/j.tetlet.2005.09.085

  日期：2005.11

  Functionalised hydroxy alpha-alkynones were transformed to the corresponding spiroketals by a one-pot cascade consisting of palladium-catalysed hydrogenation of the triple bond, hydroxyl group deprotection and spirocyclisation under mild nonacidic conditions. The reaction does not rely upon thermodynamic control to set the configuration of the ketal stereocentre so that both the anomerically stabilised and nonstabilised isomers are similarly accessible. (c) 2005 Elsevier Ltd. All rights reserved.