dimethyl 2-pent-4-enyl-2-phenylsulfanylpropanedioate | 196494-61-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: dimethyl 2-pent-4-enyl-2-phenylsulfanylpropanedioate
• CAS: 196494-61-8
• 化学式: C₁₆H₂₀O₄S
• 分子量: 308.398
• InChiKey: IKQYNHSHRNRXNC-UHFFFAOYSA-N

物化性质

• 沸点：
  404.4±45.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  21.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  dimethyl 2-pent-4-enyl-2-phenylsulfanylpropanedioate 在 4-二甲氨基吡啶 、 氢氧化钾 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 16.0h， 生成 2-Phenylsulfanyl-hept-6-enoic acid methyl ester
  参考文献：
  名称：

  A Model Study of Intramolecular Asymmetric Radical Cyclizations of α-Ester and α-Amide Radicals

  摘要：

  AbstractStarting from malonate, a practical route was developed for the synthesis of α‐phenylthio acid 3. Several chiral compounds including (‐)‐menthol, (‐)‐8‐pbenylmenthol and a camphor based oxazolidinone 8 reacted with 3 to give α‐phenylthio esters or amide. These sulfides cyclized efficiently when reacted with tributyltin hydride. Among the chiral auxiliaries used, 8‐phenylmenthyl group displayed moderate asymmetric induction (64% ee for cis‐product and 40% ee for trans‐product). Based on this results, a transition state model was proposed to explain the observed stereoselectivity. In this model, due to π,π‐orbital overlap of the phenyl ring and the carbonyl, the si‐face of the most stable conformer of the radical was shielded. This controlled the carbon‐carbon bond formation to occur from the re‐face.

  DOI：

  10.1002/jccs.199700039
• 作为产物：
  描述：

  丙二酸二甲酯 在 sodium methylate 、 sodium hydride 作用下， 生成 dimethyl 2-pent-4-enyl-2-phenylsulfanylpropanedioate
  参考文献：
  名称：

  Stereogenic reactions of the α-carbon radicals of 8-phenylmenthyl esters

  摘要：

  描述了 8-苯基苯甲酯的立体选择性自由基还原和环化过程；主要产物被认为来自于具有与酯的烷氧基对立的较大取代基构象的过渡态。

  DOI：

  10.1039/c39910001603

文献信息

• A Model Study of Intramolecular Asymmetric Radical Cyclizations of α-Ester and α-Amide Radicals
  作者：Ru-Long Yeh、Weir-Tom Jiaang、Yeun-Min Tsai

  DOI：10.1002/jccs.199700039

  日期：1997.6

  AbstractStarting from malonate, a practical route was developed for the synthesis of α‐phenylthio acid 3. Several chiral compounds including (‐)‐menthol, (‐)‐8‐pbenylmenthol and a camphor based oxazolidinone 8 reacted with 3 to give α‐phenylthio esters or amide. These sulfides cyclized efficiently when reacted with tributyltin hydride. Among the chiral auxiliaries used, 8‐phenylmenthyl group displayed moderate asymmetric induction (64% ee for cis‐product and 40% ee for trans‐product). Based on this results, a transition state model was proposed to explain the observed stereoselectivity. In this model, due to π,π‐orbital overlap of the phenyl ring and the carbonyl, the si‐face of the most stable conformer of the radical was shielded. This controlled the carbon‐carbon bond formation to occur from the re‐face.
• Stereogenic reactions of the α-carbon radicals of 8-phenylmenthyl esters
  作者：Ming-Yi Chen、Jim-Min Fang、Yeun-Min Tsai、Ru-Long Yeh

  DOI：10.1039/c39910001603

  日期：——

  The stereoselective free-radical type reduction and cyclisation of 8-phenylmenthyl esters is described; the predominant products are considered to be derived from the transition states with conformations having the larger substituent anti to the alkoxy group of the ester.

  描述了 8-苯基苯甲酯的立体选择性自由基还原和环化过程；主要产物被认为来自于具有与酯的烷氧基对立的较大取代基构象的过渡态。