(1SR,4aRS,8aRS)-9-methyleneoctahydro-1H-1,4a-(epoxymethano)naphthalene | 4752-31-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: (1SR,4aRS,8aRS)-9-methyleneoctahydro-1H-1,4a-(epoxymethano)naphthalene
• CAS: 4752-31-2
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: OFBMEALCCXHYMG-IJLUTSLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.26
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1SR,4aRS,8aRS)-9-methyleneoctahydro-1H-1,4a-(epoxymethano)naphthalene 在 硫酸 作用下， 以 乙醚 为溶剂， 反应 2.5h， 以51%的产率得到(±)-1-((1R*,4aS*,8aS*)-1-hydroxydecahydronaphthalen-4ayl)ethanone
  参考文献：
  名称：

  Concise Synthesis of 1,4a-Bifunctionalised Decalin Building Blocks by C-H Activation of Decalin

  摘要：

  十氢萘的Friedel-Crafts酰化作用在C1和C4a位引入功能性基团，这些基团可以进一步发展为新型构建模块，其在环接点处具有甲基酮、甲基醇或乙烯基团。

  DOI：

  10.1055/s-0030-1261184
• 作为产物：
  描述：

  2,3,5,6,7,8-hexahydro-1H-azulen-4-one 在 盐酸 、 aluminum (III) chloride 、 锌 作用下， 以 水 、 1,2-二氯乙烷 为溶剂， 100.0 ℃ 、101.33 kPa 条件下， 反应 8.0h， 生成 (1SR,4aRS,8aRS)-9-methyleneoctahydro-1H-1,4a-(epoxymethano)naphthalene
  参考文献：
  名称：

  用三氯化铝-乙酰氯进行脂肪CH-H活化：扩大Baddeley反应的范围，以饱和烃官能化†

  摘要：

  的功能化 十氢化萘Baddeley等人在50年前就报道了通过“脂肪族Friedel-Crafts”反应。该协议在C–H活化的背景下具有当前意义，在这里我们证明了其对一系列其他饱和烃的适用性。描述了产品的结构说明，并给出了其形成的机理原理。“脂肪族Friedel-Crafts”工艺可以从丰富的烃类中生产出新型的含氧结构单元，因此可以认为它一步就可以增加重要的合成价值。

  DOI：

  10.1039/c2ob26765a

文献信息

• C–H Functionalization of sp³ Centers with Aluminum: A Computational and Mechanistic Study of the Baddeley Reaction of Decalin
  作者：Catherine L. Lyall、Makoto Sato、Mario Uosis-Martin、Syeda Farina Asghar、Matthew D. Jones、Ian H. Williams、Simon E. Lewis

  DOI：10.1021/ja5062246

  日期：2014.10.1

  undergoes reaction with aluminum trichloride and acetyl chloride to form a tricyclic enol ether in good yield, as first reported by Baddeley. This eye-catching transformation, which may be considered to be an aliphatic Friedel-Crafts reaction, has not previously been studied mechanistically. Here we report experimental and computational studies to elucidate the mechanism of this reaction. We give supporting

  如 Baddeley 首次报道，十氢化萘与三氯化铝和乙酰氯反应生成三环烯醇醚，收率良好。这种引人注目的转变可能被认为是脂肪族 Friedel-Crafts 反应，此前尚未对其进行机械研究。在这里，我们报告了实验和计算研究，以阐明该反应的机制。我们为以下命题提供了支持证据，即在不饱和度不存在的情况下，酰基离子充当氢化物受体，形成叔碳正离子。失去一个质子会引入一个烯烃，它与另一个酰基离子反应。协调一致的 1,2-氢化物转变/氧鎓形成，然后消除，导致形成观察到的产物。
• Acylation of alkenes generated in situ by hydride transfer from isoalkanes. Synthesis of pentalenones, hydrindenones, and cyclopentenones
  作者：Christophe Morel-Fourrier、Jean Pierre Dulcere、Maurice Santelli

  DOI：10.1021/ja00021a036

  日期：1991.10

  Acylation, in the presence of AlCl3 and hydride acceptor, of methylcyclopentane, methylcyclohexane, and 2-methylbutane by ethylenic acyl chlorides, in CH2Cl2 solution, respectively, leads to tetrahydropentalenones, tetrahydroindenones, and cyclopentenones in good yields. Hydride acceptor may be either acetyl chloride or the alkenoyl chloride itself. Better results are performed in the presence of nitromethane and CuSO4. Overall yields are better than those obtained by the two-step process involving acylation of alkenes by alkenoyl chlorides and subsequent Nazarov cyclization of the resulting divinylketones. Methyl 1,4-migration is observed during the acylation of 2-methylbutane by sorboyl chloride. The mechanism of these conversions is discussed on the basis of results observed with cyclohexane-d12 and methylbutane-d6 as well as stereochemical studies of the cyclization process.
• A Model System for the Synthesis of Complanadine Alkaloids by “Diverted Kondrat’eva” Oxazole–Olefin Cycloaddition
  作者：Mario Uosis-Martin、G. Dan Pantoş、Mary F. Mahon、Simon E. Lewis

  DOI：10.1021/jo401014n

  日期：2013.6.21

  A synthetic approach to complanadine alkaloids is described which employs a Kondrat'eva reaction to construct the pyridine rings. The viability of this approach is demonstrated by its application to a model substrate accessed from unfunctionalized decalin. The key transformation affords the desired tetracyclic architecture with unprecedented incorporation of substituents on the pyridine ring, implicating the oxazole a-hydroxy group as an active participant in the cycloadduct fragmentation process.
• 909. Further reactions of 10-acetyl-Δ¹⁽⁹⁾-octalin
  作者：G. Baddeley、E. K. Baylis

  DOI：10.1039/jr9650004933

  日期：——