(-)-trans-2-<1-(2-Naphthyl)-1-methylethyl>cyclohexanol | 150577-51-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (-)-trans-2-<1-(2-Naphthyl)-1-methylethyl>cyclohexanol
• 英文别名: (1S,2R)-2-<1-(2-naphthyl)-1-methylethyl>cyclohexanol；(1S,2R)-2-(2-naphthalen-2-ylpropan-2-yl)cyclohexan-1-ol
• CAS: 150577-51-8
• 化学式: C₁₉H₂₄O
• 分子量: 268.399
• InChiKey: HBGKYJZWOCHFPU-ROUUACIJSA-N

物化性质

• 沸点：
  414.9±14.0 °C(Predicted)
• 密度：
  1.074±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (-)-trans-2-<1-(2-Naphthyl)-1-methylethyl>cyclohexanol 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 20.0~25.0 ℃ 、1399.99 MPa 条件下， 反应 32.0h， 生成 (1S,2R,3S)-2-<1-(2-naphthyl)-1-methylethyl>cyclohexyl 3-(diphenylmethylamino)butyrate
  参考文献：
  名称：

  Investigating the π-Facial Discrimination Phenomenon in the Conjugate Addition of Amines to Chiral Crotonates:  A Convenient Basis for the Rational Design of Chiral Auxiliaries

  摘要：

  This paper is concerned with the nature of the chiral inducer in the high pressure-induced conjugate addition of amines to auxiliary-tethered crotonates. Almost complete stereocontrol was obtained in the addition of diphenylmethanamine to crotonates derived from the ''arylmenthol'' auxiliaries 18a, 18c, and 4 bearing an o-methoxyphenyl, p-phenoxyphenyl, or beta-naphthyl substituent, respectively. This high efficiency has been attributed to the predominance of stacked conformations in such crotonates, a hypothesis supported by the H-1 NMR spectra, calculated energy of conformational optima of the corresponding crotonates, and X-ray crystal structure of 5a. The arene and enoate appendages are roughly coplanar, separated by 3.4-4 Angstrom. In contrast, only moderate selectivities could be achieved using various trans-2-arylcyclohexanols (27, 28, 2c, 29) as auxiliaries. In these cases the efficiency appears to be seriously compromised by the ''widening V'' arrangement exhibited by the two pi-systems, as shown in the X-ray crystal structures of crotonates 5 h and 5 k. The sense of stereochemical induction of this conjugate addition has been determined by condensing diphenylmethanamine with enantiopure crotonate (+)-5a. The adduct 9a was converted to amino alcohol (S)-11, of known configuration. This correlation is consistent with the preferential attack of the amine to the less sterically hindered enoate pi-face of(+)-5a, in its s-trans conformation. Finally, the stereochemistry of the proton transfer was determined by adding N,N-dideuteriodiphenylmethanamine to crotonate (+/-)-5a. The stereochemical outcome of this addition is consistent with the anti-addition of the incoming nitrogen nucleophile and the deuterium atom.

  DOI：

  10.1021/jo951414r
• 作为产物：
  描述：

  (1R)-2-(2-naphthalen-2-ylpropan-2-yl)cyclohexan-1-ol 以46%的产率得到
  参考文献：
  名称：

  Comins Daniel L., Salvador James M., J. Org. Chem., 58 (1993) N 17, S 4656- 4661

  摘要：

  DOI：

文献信息

• Efficient synthesis and resolution of trans-2-(1-aryl-1-methylethyl)cyclohexanols: practical alternatives to 8-phenylmenthol
  作者：Daniel L. Comins、James M. Salvador

  DOI：10.1021/jo00069a031

  日期：1993.8

  A short synthesis and resolution of effective chiral auxiliaries of the 8-arylmenthol-type were achieved using inexpensive materials, a recyclable lipase, and easily applied procedures that are amenable to large-scale preparation. A variety of isopropylarenes were alpha-metalated with n-butyllithium/potassium tert-pentoxide and treated with cyclohexene oxide to provide racemic trans-2-(1-aryl-1-methylethyl)-cyclohexanols 6a-f in fair to high yield. Candida rugosa lipase and lauric acid were used to resolve these racemic alcohols by converting the (-)-enantiomer to its laurate ester. The enzymatic resolutions were carried out at 40-degrees-C and were faster in cyclohexane than in hexanes. The synthesis and resolution of racemic trans-2-(1-methyl-1-phenylethyl)cyclohexanol (6a) were performed on a 1 mol scale in 68% overall yield, requiring three steps for (+)-6a and five steps for (-)-6a.