(S)-3-(4-chloro-phenyl)pentanedioic acid monobenzyl ester | 865367-01-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: (S)-3-(4-chloro-phenyl)pentanedioic acid monobenzyl ester
• 英文别名: (S)-3-(4-chlorophenyl)-glutaric acid monobenzyl ester；(3S)-3-(4-chlorophenyl)-5-oxo-5-phenylmethoxypentanoic acid
• CAS: 865367-01-7
• 化学式: C₁₈H₁₇ClO₄
• 分子量: 332.784
• InChiKey: KWFILWIULRFQQF-HNNXBMFYSA-N

物化性质

• 熔点：
  126 °C(Solv: ethyl ether (60-29-7); hexane (110-54-3))
• 沸点：
  494.6±40.0 °C(Predicted)
• 密度：
  1.280±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-3-(4-chloro-phenyl)pentanedioic acid monobenzyl ester 在 锂硼氢 、 potassium tert-butylate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.0h， 生成 (4R)-4-(4-chlorophenyl)tetrahydro-2H-pyran-2-one
  参考文献：
  名称：

  Enzymatic desymmetrization of 3-arylglutaric acid anhydrides

  摘要：

  Optically active (R)- and (S)-3-arylglutaric acid monoesters 3 were synthesized in quantitative yields and good stereoselectivities by lipase-catalyzed desymmetrization of the corresponding 3-arylglutaric anhydrides 2 with alcohols. It was observed that the stereochemical outcome of the reaction was influenced by the substituents present on the aromatic ring. The influence of the enzyme, alcohol, and solvent was systematically examined. Absolute configurations of the monoesters 3 were assigned by chemical correlation to corresponding lactones 4. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.06.025
• 作为产物：
  描述：

  4-氯苯甲醛 在 哌啶 、 Novozym 435 、 乙酰氯 作用下， 以 异丙醚 为溶剂， 反应 870.0h， 生成 (S)-3-(4-chloro-phenyl)pentanedioic acid monobenzyl ester
  参考文献：
  名称：

  Enzymatic desymmetrization of 3-arylglutaric acid anhydrides

  摘要：

  Optically active (R)- and (S)-3-arylglutaric acid monoesters 3 were synthesized in quantitative yields and good stereoselectivities by lipase-catalyzed desymmetrization of the corresponding 3-arylglutaric anhydrides 2 with alcohols. It was observed that the stereochemical outcome of the reaction was influenced by the substituents present on the aromatic ring. The influence of the enzyme, alcohol, and solvent was systematically examined. Absolute configurations of the monoesters 3 were assigned by chemical correlation to corresponding lactones 4. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.06.025

文献信息

• One catalyst for both enantiomers: uncovering the inversion of enantioselectivity in cinchona-mediated desymmetrization of glutaric meso-anhydrides
  作者：Trpimir Ivšić、Jurica Novak、Nađa Došlić、Zdenko Hameršak

  DOI：10.1016/j.tet.2012.07.035

  日期：2012.9

  protocol the same catalyst produces the opposite enantiomer. This occurrence was rationalized by an extensive computational study of the interactions governing the molecular complexes formed by quinine, methanol, 3-methylglutaric anhydride, and the acetic acid. It was found that in a quinine catalyzed reaction the alcohol and the anhydride were directly hydrogen bonded to the catalyst. On the other hand

  在奎宁介导的戊二酸内消旋酸酐的不对称化过程中，发现对映体选择性取决于催化剂的负载，令人费解。这项研究提出了通过添加多达合成有用水平的羧酸添加剂来改善催化路径的方法。发现在室温（rt）下利用0.1当量生物碱和and吨-9-羧酸的新颖方案可与在-30℃下需要1.1当量生物碱的方案相媲美。因此，通过改变方案，相同的催化剂产生相反的对映异构体。 通过对由奎宁，甲醇，3-甲基戊二酸酐和乙酸形成的分子配合物的相互作用进行广泛的计算研究，可以合理地解释这种情况。发现在奎宁催化的反应中，醇和酸酐直接氢键合到催化剂上。另一方面，在与添加剂的反应中，酸插在醇和奎宁之间。由于这种插入，醇从相反的面接近酸酐，这与观察到的对映选择性相反