(1R*,2S*)-2-(2-naphthyl)cyclohexyl (E)-2-butenoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (1R*,2S*)-2-(2-naphthyl)cyclohexyl (E)-2-butenoate
• 英文别名: [(1R,2S)-2-naphthalen-2-ylcyclohexyl] (E)-but-2-enoate
• 化学式: C₂₀H₂₂O₂
• 分子量: 294.393
• InChiKey: OUUJHVPEFMEPFT-MIDRKJHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R*,2S*)-2-(2-naphthyl)cyclohexyl (E)-2-butenoate 、 二苯甲胺 以 甲醇 为溶剂， 20.0 ℃ 、1399.99 MPa 条件下， 反应 18.0h， 以70%的产率得到(1R*,2S*,3RS*)-2-(2-naphthyl)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：

  巴豆酸 、 (1R*,2S*)-2-(2-naphthyl)cyclohexanol 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 以88%的产率得到(1R*,2S*)-2-(2-naphthyl)cyclohexyl (E)-2-butenoate
  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

文献信息

• 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
  作者：Françoise Dumas、Brahim Mezrhab、Jean d'Angelo、Claude Riche、Angèle Chiaroni

  DOI：10.1021/jo951414r

  日期：1996.1.1

  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.