(S)-4-cyano-4-(3',4'-dichlorophenyl)cyclohex-1-enyl | 303728-37-2

• 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: (S)-4-cyano-4-(3',4'-dichlorophenyl)cyclohex-1-enyl
• 英文别名: (S)-4-Cyano-4-(3',4'-dichlorophenyl)cyclohex-1-enyl acetate；[(4S)-4-cyano-4-(3,4-dichlorophenyl)cyclohexen-1-yl] acetate
• CAS: 303728-37-2
• 化学式: C₁₅H₁₃Cl₂NO₂
• 分子量: 310.18
• InChiKey: DAOVNQVBRYMUPR-HNNXBMFYSA-N

物化性质

• 沸点：
  461.3±45.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-4-cyano-4-(3',4'-dichlorophenyl)cyclohex-1-enyl 在 臭氧 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以60%的产率得到(S)-(-)-methyl 4-cyano-4-(3',4'-dichlorophenyl)-6-oxo-hexanoate
  参考文献：
  名称：

  Chemoenzymatic synthesis of a non-peptide tachykinin NK-2 antagonist

  摘要：

  The synthesis of a tachykinin NK-2 antagonist (S)-11 has been carried out in four steps starting from the the (S)-(+)-enol acetate 3, which was obtained in 100% e.e. by resolution of the racemic eater with Pseudomonas fluorescens lipase. The absolute configuration of the enol acetate (+)-3 was confirmed by X-ray analysis of the camphanyl derivative 13. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01149-7
• 作为产物：
  描述：

  4-氰-4-(3,4-二氯苯)环己酮 在 lipase from Pseudomonas fluorescens 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 正丁醇 为溶剂， 反应 3.0h， 生成 (S)-4-cyano-4-(3',4'-dichlorophenyl)cyclohex-1-enyl
  参考文献：
  名称：

  一锅解旋从前手性环己酮衍生的烯醇乙酸酯

  摘要：

  使用荧光假单胞菌脂肪酶和叔丁醇钾/乙酸异丙烯酯的组合，开发了一种用于从手性4,4-二取代的环己酮2衍生的烯醇式乙酸酯1脱除油的单罐方法，从而得到对映体纯的烯醇式乙酸酯（S）-1，产率为82％。基于脂肪酶（E）的固有对映选择性的计算允许在回收酮之前估算每个酶步骤的最佳理论转化率。

  DOI：

  10.1016/s0040-4039(01)01156-x

文献信息

• Desymmetrisation of 4,4-disubstituted cyclohexanones by enzyme-catalysed resolution of their enol acetates
  作者：Graham Allan、Andrew J. Carnell、Maria Luisa Escudero Hernandez、Alan Pettman

  DOI：10.1039/b005466f

  日期：——

  Enol acetates 3–10 derived from prochiral 4,4-disubstituted cyclohexanones can be resolved with Pseudomonas fluorescens lipase to give enantiomerically pure (>99% ee) enol esters by transesterification with n-BuOH. The product ketones are prochiral and can easily be recycled giving an overall desymmetrisation of the ketone. Highest selectivity was obtained for substrates containing a 4-cyano and 4-aryl or a 4-benzyloxy substituent. The methodology was compared to asymmetric deprotonation–enolate trapping using the chiral base (S,S)-bis(α-methylbenzyl)amide which gave low (54–64%) ee’s for this class of ketones.

  来自对称的4,4-二取代环己酮的醇乙酸酯3-10可以通过荧光假单胞菌脂肪酶进行分离，以转酯化反应与正丁醇生成对映体纯度>99% ee的醇酯。生成的酮是对称的，可以很容易地循环利用，从而实现酮的整体去对称化。对于含有4-氰基和4-芳基或4-苄氧基取代基的底物，获得了最高的选择性。该方法与使用手性碱(S,S)-双(α-甲基苯甲酰)胺的非对称去质子化-烯醇捕获进行了比较，该方法在这一类酮中获得了较低的对映体纯度(54-64% ee)。
• Chemoenzymatic synthesis of a tachykinin NK-2 antagonist
  作者：Graham Allan、Andrew J Carnell、Maria Luisa Escudero Hernandez、Alan Pettman

  DOI：10.1016/s0040-4020(01)00796-7

  日期：2001.9

  A non-peptide tachykinin antagonist has been synthesized in a short and efficient four step sequence starting from a chiral enol acetate, which was obtained in enantiomerically pure form by resolution using a lipase catalysed transesterification reaction. The biotransformation was optimized in terms of solvent, temperature and immobilization method used. Oxidative cleavage of the (+)-enol acetate to give the key aldehyde ester intermediate could be achieved indirectly by oxidative rearrangement to an enone followed by Baeyer-Villiger oxidation and ring opening, or by epoxidation, rearrangement and oxidative cleavage or most directly by ozonolysis. X-Ray crystallographic analysis of a camphanic ester derivative of an ester alcohol confirmed that the absolute configuration of the enol acetate was (S). (C) 2001 Published by Elsevier Science Ltd.
• Chemoenzymatic synthesis of a non-peptide tachykinin NK-2 antagonist
  作者：Andrew J Carnell、Maria Luisa Escudero Hernandez、Alan Pettman、Jamie F Bickley

  DOI：10.1016/s0040-4039(00)01149-7

  日期：2000.8

  The synthesis of a tachykinin NK-2 antagonist (S)-11 has been carried out in four steps starting from the the (S)-(+)-enol acetate 3, which was obtained in 100% e.e. by resolution of the racemic eater with Pseudomonas fluorescens lipase. The absolute configuration of the enol acetate (+)-3 was confirmed by X-ray analysis of the camphanyl derivative 13. (C) 2000 Elsevier Science Ltd. All rights reserved.
• One-pot deracemisation of an enol acetate derived from a prochiral cyclohexanone
  作者：Graham R Allan、Andrew J Carnell、Wolfgang Kroutil

  DOI：10.1016/s0040-4039(01)01156-x

  日期：2001.8

  method for the deracemisation of the enol acetate 1 derived from the prochiral 4,4-disubstituted cyclohexanone 2 has been developed using the combination of Pseudomonas fluorescens lipase and potassium t-butoxide/isopropenyl acetate to give the enantiomerically pure enol acetate (S)-1 in 82% yield. Calculations based on the inherent enantioselectivity of the lipase (E) allowed an estimation of the optimum

  使用荧光假单胞菌脂肪酶和叔丁醇钾/乙酸异丙烯酯的组合，开发了一种用于从手性4,4-二取代的环己酮2衍生的烯醇式乙酸酯1脱除油的单罐方法，从而得到对映体纯的烯醇式乙酸酯（S）-1，产率为82％。基于脂肪酶（E）的固有对映选择性的计算允许在回收酮之前估算每个酶步骤的最佳理论转化率。