2-methylene-5-methyladamantane | 155396-29-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2-methylene-5-methyladamantane
• 英文别名: 1-Methyl-4-methyleneadamantane；1-Methyl-4-methylideneadamantane
• CAS: 155396-29-5
• 化学式: C₁₂H₁₈
• 分子量: 162.275
• InChiKey: HREPUWCTJGCDDS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-methylene-5-methyladamantane 在 sodium tetrahydroborate 、 (CH₃)3S 、 臭氧 作用下， 反应 1.0h， 生成
  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：

  5-溴-2-金刚酮 在 正丁基锂 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 2-methylene-5-methyladamantane
  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

• Importance of Entropy in the Diastereoselectivity of 5-Substituted 2-Methyladamant-2-yl Cations
  作者：Antonello Filippi、Neil A. Trout、Patrick Brunelle、William Adcock、Ted S. Sorensen、Maurizio Speranza

  DOI：10.1021/jo049481l

  日期：2004.8.1

  2-methyl-5-X-adamant-2-yl cations IX (X = CN, Cl, Br, CH3O, COOCH3, C6H5, CH3, and (CH3)3Sn) toward methanol has been investigated in the gas phase at 750 Torr and in the 40−120 °C temperature range and compared with that of IF (X = F) and ISi (X = (CH3)3Si) measured previously under similar conditions. Detailed analysis of the energy surface of the IMe (X = CH3) ion reveals that the activation barrier

  2-甲基-5-X-金刚烷基-2-基阳离子I X（X = CN，Cl，Br，CH 3 O，COOCH 3，C 6 H 5，CH 3和（CH 3）3的非对映选择性已在750 Torr的气相中和40-120°C的温度范围内研究了向甲醇的Sn），并将其与测得的I F（X = F）和I Si（X =（CH 3）3 Si）进行了比较。以前在类似条件下。I Me（X = CH 3）的能量面的详细分析离子表明，其在甲醇中的顺式加成的激活势垒明显低于抗攻击性。在40-100°C的范围内，这种不利差异会因不利的熵因素而大大减小，这些熵因素足以使I Me非对映选择性在T > 69°C时从syn变为anti。的行为我我从的明显发散我˚F和我的Si。大的不利因素熵占主导合成在反应观察到非对映选择性我˚F（X = F），尽管反焓势垒低于合成势垒。不利的熵起着与反应的作用不大我的Si（X =（CH 3）3 Si）的这反