7-methyl-7-vinyl-1,4-dioxaspiro[4.5]decane | 68269-57-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7-methyl-7-vinyl-1,4-dioxaspiro[4.5]decane
• 英文别名: 1-Ethylendioxy-3-methyl-3-vinylcyclohexan；7-Methyl-7-vinyl-1,4-dioxaspiro[4.5]decane；7-ethenyl-7-methyl-1,4-dioxaspiro[4.5]decane
• CAS: 68269-57-8
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: ZXNHGTQNUDTZTJ-UHFFFAOYSA-N

物化性质

• 沸点：
  253.3±25.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  7-methyl-7-vinyl-1,4-dioxaspiro[4.5]decane 在 jones reagent 、 硼烷四氢呋喃络合物 作用下， 生成 3-methylcyclohexanone-3-acetic acid
  参考文献：
  名称：

  Studies directed toward the total synthesis of cerorubenic acid-III. 1. Expedient construction of the tetracyclic core by oxyanionic sigmatropy

  摘要：

  A synthesis of the ABCD ring framework of cerorubenic acid-III is described. Diketone 5 was first prepared by intramolecular oxidative coupling of the dienolate 10 and then suitably desymmetrized to deliver 15b. Anionic oxy-Cope rearrangement of this intermediate resulted in construction of 18, a ketone not only having all three contiguous stereogenic centers properly established but also equipped with adequate functionality for the further elaboration of ring D. In the present effort, this thrust took the form of homologation to 21, conversion to the activated diene 22, and Diels-Alder cycloaddition to methyl acrylate at high pressure. Once it became obvious that first-formed ketone 26 greatly preferred adoption of trans stereochemistry at the ring juncture, attempts to skirt this issue were made by preparing both 29 and 32. However, these advanced intermediates proved unresponsive to conjugate reduction, and attention was therefore redirected to alternative possible means for elaboration of the eastern sector.

  DOI：

  10.1021/jo00068a019
• 作为产物：
  描述：

  3-甲基-2-环己烯-1-酮 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 3.0h， 生成 7-methyl-7-vinyl-1,4-dioxaspiro[4.5]decane
  参考文献：
  名称：

  Studies directed toward the total synthesis of cerorubenic acid-III. 1. Expedient construction of the tetracyclic core by oxyanionic sigmatropy

  摘要：

  A synthesis of the ABCD ring framework of cerorubenic acid-III is described. Diketone 5 was first prepared by intramolecular oxidative coupling of the dienolate 10 and then suitably desymmetrized to deliver 15b. Anionic oxy-Cope rearrangement of this intermediate resulted in construction of 18, a ketone not only having all three contiguous stereogenic centers properly established but also equipped with adequate functionality for the further elaboration of ring D. In the present effort, this thrust took the form of homologation to 21, conversion to the activated diene 22, and Diels-Alder cycloaddition to methyl acrylate at high pressure. Once it became obvious that first-formed ketone 26 greatly preferred adoption of trans stereochemistry at the ring juncture, attempts to skirt this issue were made by preparing both 29 and 32. However, these advanced intermediates proved unresponsive to conjugate reduction, and attention was therefore redirected to alternative possible means for elaboration of the eastern sector.

  DOI：

  10.1021/jo00068a019

文献信息

• Asymmetric Synthesis of 6′-Hydroxyarenarol: The Proposed Biosynthetic Precursor to Popolohuanone E
  作者：Rachel H. Munday、Ross M. Denton、James C. Anderson

  DOI：10.1021/jo801404u

  日期：2008.10.17

  The first synthesis of (+)-6'-hydroxyarenarol 3, the proposed biogenetic precursor to popolohuanone E (1), is described. An enantioselective route to key iodide intermediate 12 has been developed allowing the asymmetric synthesis of the known cis-decalin 22. Conditions which allow the removal of the methyl ether protecting groups on the hydroxyarene leaving the exocyclic methylene moiety in tact have

  描述了（+）-6'-羟基芳烃3的首次合成，这是拟定的Popolohuanone E（1）的生物遗传前体。已经开发了对关键碘化物中间体12的对映选择性路线，从而允许不对称合成已知的顺式十氢萘22。已经开发了条件，该条件允许去除羟基芳烃上的甲基醚保护基，而使环外亚甲基部分保持完整。这个综合。
• Total syntheses of lindenane-type sesquiterpenoids: (±)-chloranthalactones A, B, F, (±)-9-hydroxy heterogorgiolide, and (±)-shizukanolide E
  作者：Guizhou Yue、Li Yang、Changchun Yuan、Biao Du、Bo Liu

  DOI：10.1016/j.tet.2012.09.053

  日期：2012.11

  Chloranthalactones A, B, F, 9-hydroxy heterogorgiolide, and shizukanolide E are a family of natural lindenane-type sesquiterpenoids isolated mainly from chloranthaceae. A general synthetic strategy was accomplished by us for the racemic total syntheses of the five natural products. The key steps included substrate-controlled Matteson epoxidation of ketone and highly diastereoselective intramolecular

  Chloranthalactones A，B，F，9-羟基杂果内酯和shizukanolide E是一类主要从桔梗科中分离的天然林丹型倍半萜类化合物。我们完成了对五个天然产物的外消旋总合成的一般合成策略。关键步骤包括酮的基质控制的Matteson环氧化和高度非对映选择性的分子内Hodgson环丙烷化反应，以构建具有挑战性的顺式，反式-3/5/6三环骨架，以及开发用于γ-亚烷基丁烯化物环形成的方法。
• Studies directed toward the total synthesis of cerorubenic acid-III. 1. Expedient construction of the tetracyclic core by oxyanionic sigmatropy
  作者：Leo A. Paquette、Marc Andre Poupart

  DOI：10.1021/jo00068a019

  日期：1993.7

  A synthesis of the ABCD ring framework of cerorubenic acid-III is described. Diketone 5 was first prepared by intramolecular oxidative coupling of the dienolate 10 and then suitably desymmetrized to deliver 15b. Anionic oxy-Cope rearrangement of this intermediate resulted in construction of 18, a ketone not only having all three contiguous stereogenic centers properly established but also equipped with adequate functionality for the further elaboration of ring D. In the present effort, this thrust took the form of homologation to 21, conversion to the activated diene 22, and Diels-Alder cycloaddition to methyl acrylate at high pressure. Once it became obvious that first-formed ketone 26 greatly preferred adoption of trans stereochemistry at the ring juncture, attempts to skirt this issue were made by preparing both 29 and 32. However, these advanced intermediates proved unresponsive to conjugate reduction, and attention was therefore redirected to alternative possible means for elaboration of the eastern sector.