(2S,1'R,2'S)-6-methoxy-2-methyl-2-naphthaleneacetic acid 2'-<1-(2-naphthyl)-1-methylethyl>cyclohexyl ester

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (2S,1'R,2'S)-6-methoxy-2-methyl-2-naphthaleneacetic acid 2'-<1-(2-naphthyl)-1-methylethyl>cyclohexyl ester
• 英文别名: [(1S,2R)-2-(2-naphthalen-2-ylpropan-2-yl)cyclohexyl] (2S)-2-(6-methoxynaphthalen-2-yl)propanoate
• 化学式: C₃₃H₃₆O₃
• 分子量: 480.647
• InChiKey: ANCMGQBJSUBOCR-QDSNVRCDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 重原子数：
  36
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,1'R,2'S)-6-methoxy-2-methyl-2-naphthaleneacetic acid 2'-<1-(2-naphthyl)-1-methylethyl>cyclohexyl ester 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以95%的产率得到(-)-trans-2-<1-(2-Naphthyl)-1-methylethyl>cyclohexanol
  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：

  (S)-2-(6-甲氧基-2-萘基)丙酰氯 、 (1R^*,2S^*)-2-<1-(2-naphthyl)-1-methylethyl>cyclohexanol 在 吡啶 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以34%的产率得到(2S,1'R,2'S)-6-methoxy-2-methyl-2-naphthaleneacetic acid 2'-<1-(2-naphthyl)-1-methylethyl>cyclohexyl ester
  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.