1-Iodo-4-methylene-adamantane | 155396-28-4

• 分子结构分类: 有机化合物
• 英文名称: 1-Iodo-4-methylene-adamantane
• CAS: 155396-28-4
• 化学式: C₁₁H₁₅I
• 分子量: 274.145
• InChiKey: DKOMDDRBSVFINF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.56
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1-Iodo-4-methylene-adamantane 在 盐酸 作用下， 以 硝基甲烷 为溶剂， 反应 1.0h， 生成 (1S,3R,4R,5S)-4-Chloro-1-iodo-4-methyl-adamantane 、 (1S,3S,4S,5R)-4-Chloro-1-iodo-4-methyl-adamantane
  参考文献：
  名称：

  Electrostatic vs Hyperconjugative Effects as Stereoinductive Factors in the Adamantane Ring System

  摘要：

  A series of 5-substituted (X) adamant-2-yl derivatives 1 (Y = O and CH2) have been synthesized and their C-13 NMR spectra measured. The carbonyl and ethylenic C-13 substituent chemical shifts (SCS) are shown to be proportional to substituent field effects (sigma(F)). By use of the polar field susceptibility parameter (rho(F)) for the former shifts, polar field parameters (Delta sigma(F) values) have been calculated for a series of p-SC6H4 substituents. II-Facial diastereoselectivities for the reduction (NaBH4) and methylation (MeLi) of para-substituted (S) phenyl derivatives of 1 (Y = O; X = p-SC6H4) and, as well, for the hydrochlorination of similarly substituted alkenes 1 (Y = CH2; X = p-SC6H4) have been determined and correlated successfully against polar field parameters (Delta sigma(F) values). The slopes of these plots (log(10)[Z]/[E] vs Delta sigma(F)) provide polar-field susceptibility parameters (rho(FS)) which have been deployed to calculate appropriate diastereoselectivities of the aforementioned reactions for 5-substituted (X) derivatives of 1 (Y = O and CH2) in general. A comparison of these calculated values with observed diastereoselectivities for a wide range of substituents reveals that direct electrostatic field interactions play a dominant role in governing the phenomena for nucleophilic additions of the ketones 1 (Y = O) and that it is unnecessary to invoke Cieplak's transition-state hyperconjugative model. This appears to be also the case for electrophilic additions to 1 (Y = CH2) not involving final nucleophilic capture of an intermediate cation. However, hyperconjugation clearly impinges significantly on II-facial diastereoselectivity for those reactions mediated by 2-adamantyl cations. New results for methyl-substituted derivatives of 1 (Y = O and CH2, X = CH3) reinforces the sigma-electron-withdrawing character of this substituent with respect to gamma- and delta-interactions in the neutral ground-state and cationic species.

  DOI：

  10.1021/jo00086a044
• 作为产物：
  描述：

  甲基三苯基碘化膦 、 5-碘-2-金刚烷酮 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 生成 1-Iodo-4-methylene-adamantane
  参考文献：
  名称：

  Electrostatic vs Hyperconjugative Effects as Stereoinductive Factors in the Adamantane Ring System

  摘要：

  A series of 5-substituted (X) adamant-2-yl derivatives 1 (Y = O and CH2) have been synthesized and their C-13 NMR spectra measured. The carbonyl and ethylenic C-13 substituent chemical shifts (SCS) are shown to be proportional to substituent field effects (sigma(F)). By use of the polar field susceptibility parameter (rho(F)) for the former shifts, polar field parameters (Delta sigma(F) values) have been calculated for a series of p-SC6H4 substituents. II-Facial diastereoselectivities for the reduction (NaBH4) and methylation (MeLi) of para-substituted (S) phenyl derivatives of 1 (Y = O; X = p-SC6H4) and, as well, for the hydrochlorination of similarly substituted alkenes 1 (Y = CH2; X = p-SC6H4) have been determined and correlated successfully against polar field parameters (Delta sigma(F) values). The slopes of these plots (log(10)[Z]/[E] vs Delta sigma(F)) provide polar-field susceptibility parameters (rho(FS)) which have been deployed to calculate appropriate diastereoselectivities of the aforementioned reactions for 5-substituted (X) derivatives of 1 (Y = O and CH2) in general. A comparison of these calculated values with observed diastereoselectivities for a wide range of substituents reveals that direct electrostatic field interactions play a dominant role in governing the phenomena for nucleophilic additions of the ketones 1 (Y = O) and that it is unnecessary to invoke Cieplak's transition-state hyperconjugative model. This appears to be also the case for electrophilic additions to 1 (Y = CH2) not involving final nucleophilic capture of an intermediate cation. However, hyperconjugation clearly impinges significantly on II-facial diastereoselectivity for those reactions mediated by 2-adamantyl cations. New results for methyl-substituted derivatives of 1 (Y = O and CH2, X = CH3) reinforces the sigma-electron-withdrawing character of this substituent with respect to gamma- and delta-interactions in the neutral ground-state and cationic species.

  DOI：

  10.1021/jo00086a044

文献信息

• Nucleophilic Substitution Induced by Electron Transfer at the Bridgehead of Polycyclic Alkanes: Competition between Polar and Radical Pathways
  作者：William Adcock、Christopher I. Clark、Neil A. Trout

  DOI：10.1021/jo001638w

  日期：2001.5.1

  triptycenes react predominantly by a polar mechanism initiated by the formation of a carbanion. In the case of the halo ketones (6, Y = O, X = Br and I), a mechanistic divergence of the reaction was unexpectedly encountered. Whereas the bromo ketone provides the substitution product (6, Y = O, X = SnMe(3)) in good yield (ca. 75%), apparently by a radical pathway, the iodo ketone yields a fragmentation

  一系列2,5（或1,4）-二氢金刚烷胺（4和5，X = Y =卤素）和9,10-二卤代三烯（7，X = Y =卤素）以及两个5-卤代（X）在不存在和存在叔丁胺（TBA）和二环己基膦（DCHP）的情况下，用THF中的Me（3）SnLi处理了金刚烷-2-酮（6，Y = O，X = Br和I）。这些反应的产物分布已通过（13）C和（119）Sn NMR光谱，气相色谱分析和GC / MS建立。前一种化合物（4和5）似乎仅通过自由基链反应（S（RN）1机理）反应生成锡取代产物。相比之下，三联体主要通过形成碳负离子引发的极性机制反应。在卤代酮（6，Y = O，X = Br和I）的情况下，意外地遇到了反应的机理分歧。溴代酮显然可以通过自由基途径以高收率（约75％）提供取代产物（6，Y = O，X = SnMe（3）），而碘代酮则可以产生碎片化产物（约95％）。产量）。这种机械转换突显了离去基团的电负性以