2-(2-Adamantylidene)ethyl vinyl ether | 156421-22-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(2-Adamantylidene)ethyl vinyl ether
• 英文别名: 2-(2-vinyloxyethylidene)adamantane
• CAS: 156421-22-6
• 化学式: C₁₄H₂₀O
• 分子量: 204.312
• InChiKey: YTDAYTYELOUXFM-BNNQUZSASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  2-(2-Adamantylidene)ethyl vinyl ether 在 (1,5-cyclooctadiene)(bis(1,2-diphenylphosphino)ethane)rhodium(I) chloride 作用下， 以 苯甲腈 为溶剂， 反应 20.0h， 以49%的产率得到2-(spirocyclopentan-3'-one)adamantane
  参考文献：
  名称：

  Metal Mediated One-Pot Synthesis of Cyclopentanones from Allyl Vinyl Ethers or Diallyl Ethers via Tandem Claisen Rearrangement and Hydroacylation

  摘要：

  环戊酮 3 和环戊酮 7 分别是通过烯丙基乙烯基醚 1 和二烯丙基醚 4 一次反应生成的。转化过程在 RhCl(cod)(dppe)或 RuCl2(PPh3)3 存在下于高温下进行，包括一系列脂肪族克莱森重排和作为中间体生成的戊-4-烯烃的分子内羟基化反应。在克莱森重排之前，二烯丙基醚 4 还会发生一次双键异构化。

  DOI：

  10.1055/s-1995-3909
• 作为产物：
  描述：

  adamantylideneacetaldehyde 在 sodium tetrahydroborate 、 mercury(II) diacetate 作用下， 以 异丙醇 为溶剂， 反应 16.0h， 生成 2-(2-Adamantylidene)ethyl vinyl ether
  参考文献：
  名称：

  Face Selection in Claisen Rearrangements

  摘要：

  An investigation is reported of the stereochemistry of the Claisen rearrangement of 2-(5-phenyl-2-adamantylidene) ethyl vinyl ether (1-Ph) and of allyl (5-fluoro-2-adamantylidene) methyl ether (2-F). Both ethers undergo the rearrangement principally with the newly forming bond at the zu face (i.e., syn to the 5-substituent), showing that this bond in the transition state is electron deficient from the standpoint of both termini. The two derivatives of the latter ether in which the one remaining hydrogen has been replaced by a phenyl group or an oxide anion function (3-F and 4-F) were also examined. In these two instances as well, the zu face of the vinyl terminus is favored; in all four cases, the ratio of stereoisomers is in the range of 1.33 to 1.56. The introduction of a negative charge at this terminus evidently fails to bring about the onset of the type of delocalization envisioned in the Anh model. Taken together with the oxy-Cope and allyl vinyl sulfoxide rearrangements studied earlier, these [3,3] sigmatropic shifts all exhibit a remarkably uniform face selectivity.

  DOI：

  10.1021/jo00091a010

文献信息

• Mukherjee Ashis, Wu Gianhong, le Noble William J., J. Org. Chem, 59 (1994) N 12, S 3270-3274
  作者：Mukherjee Ashis, Wu Gianhong, le Noble William J.

  DOI：——

  日期：——
• Eilbracht Peter, Gersmeier Alexander, Lennartz Detlev, Huber Thomas, Synthesis, (1995) N 3, S 330-334
  作者：Eilbracht Peter, Gersmeier Alexander, Lennartz Detlev, Huber Thomas

  DOI：——

  日期：——