(E/Z)-5-phenyladamantan-2-ol | 373595-27-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E/Z)-5-phenyladamantan-2-ol
• 英文别名: 5-phenyladamantan-2-ol
• CAS: 373595-27-8
• 化学式: C₁₆H₂₀O
• 分子量: 228.334
• InChiKey: CNUBUIQMVZHMTJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.13
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (E/Z)-5-phenyladamantan-2-ol 在 叔丁基锂 、 硝酸 作用下， 以 四氢呋喃 、 硝基甲烷 、 乙酸酐 为溶剂， 反应 14.0h， 生成 (Z)-5-(p-Nitrophenyl)adamantan-2-yl tosylate
  参考文献：
  名称：

  Face selection in the reduction of p,p'-disubstituted 5,7-diphenyl-2-adamantanones and hydrolysis of the corresponding 2-adamantyl tosylates

  摘要：

  The reduction of 5,7-diphenyl-2-adamantanone with sodium borohydride in 2-propanol is affected by the introduction of a p-nitro substituent in one of the rings: the E-alcohol is obtained in small but easily measurable excess of 1.30:1. Conversely, the introduction of a p-amino group leads to an excess of Z-isomer by roughly the same factor (1.28). When both substituents are present, they evidently cooperate to produce a ratio of 1.64. The tosylates of the alcohols were prepared and their solvolysis rates measured in 3% aqueous hexafluoro-2-propanol and compared with those of the parent and p-substituted 5-phenyl-2-adamantyl tosylates. Additivity of substituent effects was again observed, but the p-aminophenyl group in these reactions was deactivating compared to phenyl, presumably due to II-bonding and/or protonation of the amino group in the acidic medium.

  DOI：

  10.1021/jo00080a012
• 作为产物：
  描述：

  5-phenyladamantan-2-one 在 tetra(n-butyl)ammonium borohydride 作用下， 以 四氢呋喃 为溶剂， 生成 (E/Z)-5-phenyladamantan-2-ol
  参考文献：
  名称：

  还原中取代基修饰对人脸选择的影响。

  摘要：

  DOI：

  10.1021/jo9721296

文献信息

• Transmission of polar substituent effects in the adamantane ring system as monitored by 19F NMR: hyperconjugation as a stereoinductive factor
  作者：William Adcock、Neil A. Trout

  DOI：10.1021/jo00010a012

  日期：1991.5

  A limited series of (E)- and (Z)-5-substituted adamant-2-yl fluorides 8 and 9, respectively, has been synthesized and characterized, and the F-19 chemical shifts have been measured in several solvents. A wide range of F-19 substituent chemical shifts (SCS, ppm) are obtained for the former system (ca. 9.1 (c-C6H12), 9.6 (CDCl3), and 11.8 (HFIP)) compared to the latter (ca. 0.6 (c-C6H12), 0.7 (CDCl3), and 2.3 (HFIP)). Factorization of the F-19 SCS into polar field (rho-F-sigma-F) and residual contributions (F-19 SCS - rho-F-sigma-F) reveals the predominance of the latter solvent-independent component for the E fluorides (8). Comparison of 8 with a similar dissection of the F-19 SCS of 4-substituted bicyclo[2.2.2]oct-1-yl fluorides 2 strongly suggests that the origin of the large residual contributions for 8 is "through-three-bond" electron delocalization or double hyperconjugation. The importance of this long-range electronic mechanism as a factor governing pi-facial diastereoselection in 2,5-disubstituted adamantanes (1) is discussed. In particular, the assertion that the p-anilino substituent is an electron donor group at remote probe or reaction sites in saturated systems is addressed.
• Face Selection in the Capture of Anionic Carbon
  作者：Vani R. Bodepudi、William J. le Noble

  DOI：10.1021/jo00091a009

  日期：1994.6

  Several reactions of 2-(5-phenyladamantyl) derivatives have been examined with the objective of determining the stereochemistry of addition of electrophiles to a trigonal center Ct carrying a full or partial negative charge. These reactions included the carbonation and bromination of the 2-lithioadamantane(s) attack at the zu face was found to be predominant. Methylation of 5-phenyl-2-adamantanone with either methyllithium or lithium dimethylcuprate gave mixtures of the methyl alcohols in which the E-isomer is the main product. Attempts to study the reactions of the enolate anion derived from the (E)- and (Z)-phenyl 2-(5-phenyladamantyl) ketones 7-Ph were not successful: bromination could not be forced at all, and methylation and protonation occur at oxygen. The enol ether and enol were studied also; brominations of these neutral species occur at the zu face. It is concluded that even the imposition of negative charge upon the trigonal center does not engender the type of hyperconjugation envisioned by Anh in the capture of electrophiles. Protonation of the enol ether led to an equilibrium mixture of ketones 7-Ph; protonation of the enol itself gave an excess of the E-isomer. Possible reasons for this unexpected outcome are discussed.