(E)-1-(甲氧基甲氧基)-3,7-二甲基辛-2,6-二烯 | 70473-30-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: (E)-1-(甲氧基甲氧基)-3,7-二甲基辛-2,6-二烯
• 英文名称: geraniol methoxymethyl ether
• 英文别名: geranyl methoxymethyl ether；(E)-1-(methoxymethoxy)-3,7-dimethylocta-2,6-diene；geraniol-MOM；(2E)-1-(methoxymethoxy)-3,7-dimethylocta-2,6-diene
• CAS: 70473-30-2
• 化学式: C₁₂H₂₂O₂
• 分子量: 198.305
• InChiKey: SAKWOVITFRSKER-XYOKQWHBSA-N

物化性质

• 沸点：
  254.7±28.0 °C(Predicted)
• 密度：
  0.876±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-1-(甲氧基甲氧基)-3,7-二甲基辛-2,6-二烯 在 sodium periodate 、 三乙胺 、 三甲氧基磷 作用下， 以 甲醇 、 水 为溶剂， 反应 88.17h， 生成 (2E,6E)-8-methoxymethoxy-2,6-dimethyl-octa-2,6-dien-1-ol
  参考文献：
  名称：

  Facile functionalization of the isopropylidene terminus of acyclic monoterpenes by way of benzenesulfenyl chloride addition

  摘要：

  DOI：

  10.1016/s0040-4020(01)91499-1
• 作为产物：
  描述：

  香叶醇 、 氯甲基甲基醚 在 4-二甲氨基吡啶 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以91.7%的产率得到(E)-1-(甲氧基甲氧基)-3,7-二甲基辛-2,6-二烯
  参考文献：
  名称：

  肉桂酚的不对称全合成：原始结构的修订。

  摘要：

  结构3,4-二羟基-2,4,6,8- tetramethyldec -8- enolide（1）被分配到的代谢物灰霉病，但几个合成类似物的光谱具有从的显著差异1。检查过度产生聚酮化合物的灰质芽孢杆菌突变体的成分，得到足够量的1（现在称为cintotolide）用于化学转化。这些导致了代谢物的γ-丁内酯结构的改变。这种结构已经通过不对称的全合成得到证实，该合成也确立了其绝对构型。

  DOI：

  10.1021/jo501471m

文献信息

• Highly selective one-pot conversion of THP and MOM ethers to acetates by indium triiodide-catalysed deprotection and subsequent transesterification by ethyl acetate
  作者：Brindaban C. Ranu、Alakananda Hajra

  DOI：10.1039/b104055n

  日期：——

  A simple and efficient method is developed for the chemoselective one-pot conversion of tetrahydropyranyl (THP) and methoxymethyl (MOM) ethers of primary alcohols to the corresponding acetates by indium triiodide-catalysed deprotection and subsequent acetylation by ethyl acetate through a transesterification process.

  我们开发了一种简单而高效的方法，通过铟三碘催化去保护和随后的醋酸乙酯转酯化过程，将初级醇的四氢吡喃基（THP）和甲氧基甲基（MOM）醚选择性地一锅转化为相应的醋酸酯。
• Regio- and stereoselective terminal allylic carboxymethylation of gem-dimethyl olefins. Synthesis of biologically important linear degraded terpenoids.
  作者：YUKIO MASAKI、KAZUHIKO SAKUMA、KENJI KAJI

  DOI：10.1248/cpb.33.1930

  日期：——

  gem-Dimethyl olefins (III) were transformed regiospecifically to the terminal β-methallyl sulfides (IV) bearing the methoxycarbonylmethyl substituent on the sulfur atom via (A) methoxycarbonylmethanesulfenyl chloride addition followed by dehydrochlorination or (B) allylic chlorination with SO2Cl2 followed by sulfenylation with methyl thioglycolate. Treatment of the sulfides (IV) with tert-BuOK or NaH in N, N-dimethylformamide or dimethyl sulfoxide at room temperature gave stereoselectively the sulfur-free esters (V) through a novel one-pot desulfurizative [2, 3]-sigmatropic rearrangement. By utilizing this method, biologically and pharmacologically important linear degraded terpenoids, a diol component (1) of the pheromonal secretion of the queen butterfly and several ω-quinoid acids (4, n=1, 2) and (5, n=1, 2), which are metabolites of polyisoprenoidquinones, were synthesized.

  gem-Dimethyl 烯烃 (III) 通过 (A) 向甲氧基羧甲烷磺酰氯的加成反应后去氯化，或 (B) 与 SO2Cl2 的烯丙基氯化反应，再与甲基硫代甘油酸酯进行硫烯基化反应，特异性地转化为带有甲氧基羧甲基取代基的末端 β-美沙酰硫化物 (IV)。在室温下，用 tert-BuOK 或 NaH 处理这些硫化物（IV）于 N,N-二甲基甲酰胺或二甲基亚砜，得到无硫的酯 (V)，这一过程通过一种新颖的一锅式脱硫 [2,3]-σ-转位重排实现。利用该方法，合成了生物和药理学上重要的线性降解萜烯，蝴蝶女王的信息素分泌物中的二醇成分 (1)，以及几种 ω-醌酸 (4, n=1, 2) 和 (5, n=1, 2)，这些都是多异戊二烯醌的代谢物。
• Convergent total synthesis of corallocin A
  作者：Tomoya Mashiko、Yuta Nakazato、Yuta Katsumura、Akihiko Kasamatsu、Shinya Adachi、Shogo Kamo、Akinobu Matsuzawa、Kazuyuki Sugita

  DOI：10.1039/d1ob00451d

  日期：——

  The first total synthesis of corallocin A is described herein. The Suzuki coupling reaction as a key step proceeded with high stereoselectivity and in good yield. Robust transformations, including Vilsmeier–Haack formylation and Wittig reaction, allowed for effective access to corallocin A.

  本文描述了珊瑚素 A 的第一次全合成。Suzuki偶联反应作为关键步骤以高立体选择性和良好收率进行。强大的转化，包括 Vilsmeier-Haack 甲酰化和 Wittig 反应，允许有效获得珊瑚素 A。
• Convenient synthesis of decalin systems of bioactive terpenoids
  作者：Vinayak K Gore、Shailesh R Desai、T Mayelvaganan、R Padmakumar、Shreeshailkumar B Hadimani、Sujata V Bhat

  DOI：10.1016/s0040-4020(01)86353-5

  日期：1993.3

  New analogues of bioactive terpenoids, forskolin, nimbolide, isozonarol and ambrox have been synthesized using general Diels-Alder reaction of 2-formyl-4,4-dimethyl-cyclohexa-2,5-dienone (7) with 1,2-disubstituted-1,3-dienes (8a–k) which yielded endo- & exo-adducts. The deformylation, epimerisation, angular methylation, reduction and oxidation studies on these adducts have been reported.

  利用2-甲酰基-4,4-二甲基-环己-2,5-二烯酮（7）与1,2-二取代- 1,3-二烯（8a–k）产生内加合物和外加合物。已经报道了这些加合物的甲酰基化，差向异构化，甲基角化，还原和氧化研究。
• Expanded Substrate Scope and Improved Reactivity of Ether-Forming Cross-Coupling Reactions of Organotrifluoroborates and Acetals
  作者：Cam-Van T. Vo、T. Andrew Mitchell、Jeffrey W. Bode

  DOI：10.1021/ja205174c

  日期：2011.9.7

  Mixed acetals and organotrifluoroborates undergo BF3 center dot OEt2-promoted cross-couplings to give dialkyl ethers under simple, mild conditions. A survey of reaction partners identified a hydroxamate leaving group that improves the regioselectivity and product yield in the BF3 center dot OEt2-promoted coupling reaction of mixed acetals and potassium alkynyl-, alkenyl-, aryl- and heteroaryltrifluoroborates to access substituted dialkyl ethers. This leaving group enables the reaction to proceed rapidly under mild conditions (0 degrees C, 5-60 min) and permits reactions with electron-deficient potassium aryltrifluoroborates that are less reactive with other acetal substrates. A study of the reaction mechanism and characterization of key intermediates by NMR spectroscopy and X-ray crystallography identified a role for the hydroxamate moiety as a reversible leaving group that serves to stabilize the key oxocarbenium intermediate and the need for a slight excess of organodifluoroborane to serve as a catalyst. A secondary role for the boron nucleophile as an activating ligand was also considered. These studies provide the basis for a general class of reagents that lead to dialkyl ethers by a simple, predictable cross-coupling reaction.