2-(phenylthio)hept-6-enoic acid | 196494-60-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-(phenylthio)hept-6-enoic acid
• 英文别名: 2-Phenylsulfanylhept-6-enoic acid
• CAS: 196494-60-7
• 化学式: C₁₃H₁₆O₂S
• 分子量: 236.335
• InChiKey: JSEZGKCXGQKBOY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  62.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(phenylthio)hept-6-enoic acid 在 正丁基锂 、 草酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 18.67h， 生成 (1S,5R,7R)-10,10-Dimethyl-2-(2-phenylsulfanyl-hept-6-enoyl)-4-oxa-2-aza-tricyclo[5.2.1.01,5]decan-3-one
  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：

  dimethyl 2-pent-4-enyl-2-phenylsulfanylpropanedioate 在 氢氧化钾 、 oxonium 作用下， 生成 2-(phenylthio)hept-6-enoic acid
  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

• Intramolecular [2 + 2] Cycloadditions of Alkyl(phenylthio)ketenes: Total Synthesis of (+)-Sphaerodiol
  作者：Xiang Wu、Hai-Jun Wang、Yong-Shuang Huang、Wei-Dong Z. Li

  DOI：10.1021/acs.orglett.8b00407

  日期：2018.4.6

  Asymmetric total synthesis of (+)-sphaerodiol (2) has been achieved. A key step is an intramolecular [2 + 2] cycloaddition of alkyl(phenylthio)ketene for rapid assembly of the decalin ring.

  已经实现了（+）-星形二醇（2）的不对称全合成。关键步骤是烷基（苯硫基）乙烯酮的分子内[2 + 2]环加成反应，以快速组装十氢化萘环。