[2-(5-Fluoroadamantane)]spirooxetane | 156475-07-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: [2-(5-Fluoroadamantane)]spirooxetane
• 英文别名: 1-Fluorospiro[adamantane-4,2'-oxirane]
• CAS: 156475-07-9；140902-96-1；141041-75-0
• 化学式: C₁₁H₁₅FO
• 分子量: 182.238
• InChiKey: GUUIVDGSRLLYQQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [2-(5-Fluoroadamantane)]spirooxetane 在 jones reagent 、 三氟化硼乙醚 作用下， 以 苯 为溶剂， 反应 0.02h， 生成 2-金刚烷甲酸
  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 The two derivatives of the latter ether in which the one remaining hydrogen has been replaced by a phenyl group or an oxide anion function (3-F and 4-F) were also examined.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 、 trimethylsulphoxonium iodide 在 sodium hydride 作用下， 以 二甲基亚砜 为溶剂， 以76%的产率得到[2-(5-Fluoroadamantane)]spirooxetane
  参考文献：
  名称：

  通过 19 F NMR 监测的金刚烷环系统中极性取代基效应的传输

  摘要：

  一系列广泛的 (E)/(Z)-5-取代 (X)adamant-2-yl 氟化物（分别为 2 和 3）和 (E)/(Z)-4-取代 (X)adamant-1-合成并表征了基氟（分别为 4 和 5），并在几种溶剂中测量了它们的 19F 化学位移。19F 取代基化学位移 (SCS) 与极场参数 (σF) 的相关性以及与 4-取代 (X) 双环 [2.2.2] oct-1-基氟 (1) 的 19F SCS 的比较为静电场和“通过三键”电子离域（双超共轭）效应作为这些饱和系统中极性效应的长程传输模式的重要性。前一种效应不仅与空间因素（角度和距离）有关，而且与 C-F σ 键的“刚度”有关。后一种电子机制显然是调节 2 和 4 的 19F SCS 的主要因素，但由于特定的立体电子要求，在 3 和 5 中被“关闭”。©1998 John Wiley & Sons, Ltd.

  DOI：

  10.1002/(sici)1097-458x(199803)36:3<181::aid-omr250>3.0.co;2-a

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：——
• Transmission of polar substituent effects in the adamantane ring system as monitored by19F NMR
  作者：William Adcock、Neil A. Trout

  DOI：10.1002/(sici)1097-458x(199803)36:3<181::aid-omr250>3.0.co;2-a

  日期：1998.3

  of the 19F substituent chemical shifts (SCS) against polar field parameters (σF) together with comparisons against the 19F SCS of 4‐substituted(X)bicyclo[2.2.2]oct‐1‐yl fluorides (1) provide unequivocal evidence for the importance of electrostatic field and ‘through‐three‐bond’ electron delocalization (double hyperconjugation) effects as long‐range modes of transmission of polar effects in these saturated

  一系列广泛的 (E)/(Z)-5-取代 (X)adamant-2-yl 氟化物（分别为 2 和 3）和 (E)/(Z)-4-取代 (X)adamant-1-合成并表征了基氟（分别为 4 和 5），并在几种溶剂中测量了它们的 19F 化学位移。19F 取代基化学位移 (SCS) 与极场参数 (σF) 的相关性以及与 4-取代 (X) 双环 [2.2.2] oct-1-基氟 (1) 的 19F SCS 的比较为静电场和“通过三键”电子离域（双超共轭）效应作为这些饱和系统中极性效应的长程传输模式的重要性。前一种效应不仅与空间因素（角度和距离）有关，而且与 C-F σ 键的“刚度”有关。后一种电子机制显然是调节 2 和 4 的 19F SCS 的主要因素，但由于特定的立体电子要求，在 3 和 5 中被“关闭”。©1998 John Wiley & Sons, Ltd.
• 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.