2-Ethynyl-3-fluoroadamantan-2-ol | 156421-23-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Ethynyl-3-fluoroadamantan-2-ol
• 英文别名: 2-Ethynyl-5-fluoroadamantan-2-ol
• CAS: 156421-23-7
• 化学式: C₁₂H₁₅FO
• 分子量: 194.249
• InChiKey: YKQWXBHJPMKRMZ-UHFFFAOYSA-N

物化性质

• 沸点：
  265.7±40.0 °C(predicted)
• 密度：
  1.20±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Ethynyl-3-fluoroadamantan-2-ol 在 甲酸 作用下， 以76%的产率得到<2-(5-Fluoroadamantylidene)>acetaldehyde
  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 The two derivatives of the latter ether in which the one remaining hydrogen has been replaced by a phenyl group or an oxide anion function (3-F and 4-F) were also examined.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
• 作为产物：
  描述：

  5-氟-2-金刚烷酮 、 乙炔 在 氨 、 sodium amide 作用下， 以70%的产率得到2-Ethynyl-3-fluoroadamantan-2-ol
  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 The two derivatives of the latter ether in which the one remaining hydrogen has been replaced by a phenyl group or an oxide anion function (3-F and 4-F) were also examined.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：——
• Face Selection in Claisen Rearrangements
  作者：Ashis Mukherjee、Qianhong Wu、William J. le Noble

  DOI：10.1021/jo00091a010

  日期：1994.6

  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.