2-Methylene-5-phenyladamantane | 132317-57-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-Methylene-5-phenyladamantane
• 英文别名: 4-Methylidene-1-phenyladamantane
• CAS: 132317-57-8
• 化学式: C₁₇H₂₀
• 分子量: 224.346
• InChiKey: AERIAAUKIXSHRM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.53
• 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-phenyladamantane 在 间氯过氧苯甲酸 作用下， 生成 5-Phenyl-2-adamantanespirooxirane
  参考文献：
  名称：

  Electronic control of face selection in the capture of radicals

  摘要：

  A simple procedure is described which leads to the pure epimeric 2-(5-phenyl)adamantanecarboxylic acids E-1 and Z-1. Both acids upon treatment with bromine and mercuric oxide in carbon tetrachloride undergo the Hunsdiecker reaction to give the same mixture of E- and Z- 2-bromo-5-phenyladamantanes 4. 5-Phenyl-2-methyleneadamantane 6 undergoes reaction with bromotrichloromethane to give two diastereomeric adducts. In both instances, the major isomer results from the abstraction of a bromine atom by the zu face of the intermediate 5-phenyl-2-adamantyl radicals. The results mesh with other examples of face selection which we have previously ascribed to transition-state hyperconjugation. An additional case (hydride shift in a carbocation) was encountered in this work, as well as one apparent exception: the oxirane formation from adamantanone and sulfonium ylids. That result is attributed to thermodynamic control of the initial addition step.

  DOI：

  10.1021/jo00006a009
• 作为产物：
  描述：

  5-phenyladamantan-2-one 、 甲基三苯基溴化膦 在 正丁基锂 作用下， 生成 2-Methylene-5-phenyladamantane
  参考文献：
  名称：

  Electronic control of face selection in the capture of radicals

  摘要：

  A simple procedure is described which leads to the pure epimeric 2-(5-phenyl)adamantanecarboxylic acids E-1 and Z-1. Both acids upon treatment with bromine and mercuric oxide in carbon tetrachloride undergo the Hunsdiecker reaction to give the same mixture of E- and Z- 2-bromo-5-phenyladamantanes 4. 5-Phenyl-2-methyleneadamantane 6 undergoes reaction with bromotrichloromethane to give two diastereomeric adducts. In both instances, the major isomer results from the abstraction of a bromine atom by the zu face of the intermediate 5-phenyl-2-adamantyl radicals. The results mesh with other examples of face selection which we have previously ascribed to transition-state hyperconjugation. An additional case (hydride shift in a carbocation) was encountered in this work, as well as one apparent exception: the oxirane formation from adamantanone and sulfonium ylids. That result is attributed to thermodynamic control of the initial addition step.

  DOI：

  10.1021/jo00006a009

文献信息

• Electrostatic vs Hyperconjugative Effects as Stereoinductive Factors in the Adamantane Ring System
  作者：William Adcock、Jason Cotton、Neil A. Trout

  DOI：10.1021/jo00086a044

  日期：1994.4

  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.
• Burgess, Kevin; Van Der Donk, Wilfred A.; Jarstfer, Michael B., Journal of the American Chemical Society, 1991, vol. 113, # 16, p. 6139 - 6144
  作者：Burgess, Kevin、Van Der Donk, Wilfred A.、Jarstfer, Michael B.、Ohlmeyer, Michael J.

  DOI：——

  日期：——
• Face selection in thermal cycloaddition and -reversion
  作者：Haifang Li、Jack E. Silver、William H. Watson、Ram P. Kashyap、William J. Le Noble

  DOI：10.1021/jo00020a041

  日期：1991.9

  The isomer distribution has been determined in several cycloaddition reactions involving 5-fluoro- and 5-phenyladamantane derivatives in which C2 serves as one of the trigonal termini. The reactions include a [2 + 2] cycloaddition with dichloroketene, a nucleophilic addition followed by cyclization, a [2 + 2] cycloreversion of a beta-lactone, and two Diels-Alder reactions; in the latter case, the adamantane moiety was incorporated in the diene in one instance and in the dienophile in the other. In all these reactions, the reagent attacking the adamantane substrate was found to do so preferentially at the zu face, by modest but clear margins. This observation is in accord with the concept of transition-state hyperconjugation. This explanation is extended to several literature examples involving substrates with faces that are not isosteric because the polarizing group is placed closer to the site of attack; the ratios are substantial and in favor of the more hindered product in many of these examples.
• Face Selectivity in the 1,3-Dipolar Cycloaddition Reactions of Benzonitrile Oxide with 5-Substituted Adamantane-2-thiones and 2-Methyleneadamantanes
  作者：Wen-Sheng Chung、Tzong-Liang Tsai、Chia-Chin Ho、M. Y. N. Chiang、W. J. le Noble

  DOI：10.1021/jo9703717

  日期：1997.7.1

  The 1,3-dipolar cycloaddition reactions of benzonitrile oxide with 5-substituted adamantane-2-thiones (2-X) and 2-methyleneadamantanes (3-X) produced two geometrically isomeric Delta(2)-1,4,2-oxathiazolines (5-Xs) and two Delta(2)-isoxazolines (6-Xs), respectively. The substituent was varied from fluoro, chloro, bromo, to phenyl. X-ray single-crystal analysis confirmed the configuration of (Z)-5-F. The produce formation bias resulting from the favored attack of nitrile oxide on the zu-face is discussed in terms of transition-state hyperconjugation and frontier molecular orbital theory.
• BODEPUDI, VANI R.;IE, NOBLE WILLIAM J., J. ORG. CHEM., 56,(1991) N, C. 2001-2006
  作者：BODEPUDI, VANI R.、IE, NOBLE WILLIAM J.

  DOI：——

  日期：——