(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 | 196494-68-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (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
• CAS: 196494-68-5
• 化学式: C₂₃H₂₉NO₃S
• 分子量: 399.554
• InChiKey: FBNHCPZOUNIHGU-MUIVCAMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.43
• 重原子数：
  28.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  46.61
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (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 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 以17%的产率得到(1S,5R,7R)-10,10-Dimethyl-2-((1S,2S)-2-methyl-cyclopentanecarbonyl)-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：

  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