1,2,3,5,6,10b-hexahydro-8-methoxy-5-oxopyrrolo<2,1-a>isoquinoline | 123902-07-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: 1,2,3,5,6,10b-hexahydro-8-methoxy-5-oxopyrrolo<2,1-a>isoquinoline
• 英文别名: 8-methoxy-2,3,6,10b-tetrahydro-1H-pyrrolo[2,1-a]isoquinolin-5-one
• CAS: 123902-07-8
• 化学式: C₁₃H₁₅NO₂
• 分子量: 217.268
• InChiKey: WFASFPKHDSKIAM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-methoxy-N-((3-methoxyphenyl)acetyl)pyrrolidine 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 1,2,3,5,6,10b-hexahydro-8-methoxy-5-oxopyrrolo<2,1-a>isoquinoline 、 1,2,3,5,6,10b-hexahydro-10-methoxy-5-oxopyrrolo<2,1-a>isoquinoline
  参考文献：
  名称：

  Anodic amide oxidations in the presence of electron-rich phenyl rings: evidence for an intramolecular electron-transfer mechanism

  摘要：

  The anodic oxidations of amides in the presence of mono-, di-, and trialkoxyphenyl rings were examined. Although literature reduction potentials suggest that these oxidations would lead to either selective aromatic ring oxidation or mixtures, the chemoselectivity of the reactions was found to be dependent on the substitution pattern of the phenyl ring. For example, the anodic oxidations of ((3-methoxyphenyl)acetyl)pyrrolidine, ((2-methoxyphenyl)acetyl)pyrrolidine, ((3-methoxy-4-(pivaloyloxy)phenyl)acetyl)pyrrolidine, and ((3,5-dimethoxy-4-(pivaloyloxy)phenyl)acetyl)pyrrolidine all led to selective methoxylation of the pyrrolidine ring. The anodic oxidations of ((4-methoxyphenyl)acetyl)pyrrolidine and ((3,4-methoxyphenyl)acetyl)pyrrolidine led to selective methoxylation of the benzylic carbon. Mechanistic studies indicate that both amide and aryl oxidation processes compete under the reaction conditions, but that intramolecular electron transfer leads to the selective formation of products. Evidence for this mechanism was obtained by examining the cyclic voltammogram of ((3-methoxyphenyl)-acetyl)pyrrolidine, competition studies, and the preparative electrolysis of ((4-methoxyphenyl)dimethyl-acetyl)pyrrolidine. The methoxylated amides were cyclized to form tricyclic amides using titanium tetrachloride.

  DOI：

  10.1021/jo00003a029

文献信息

• An investigation into the electrophilic cyclisation of N-acyl-pyrrolidinium ions: a facile synthesis of pyrrolo-tetrahydroisoquinolones and pyrrolo-benzazepinones
  作者：Frank D. King、Abil E. Aliev、Stephen Caddick、Royston C. B. Copley

  DOI：10.1039/b907400g

  日期：——

  N-arylethyl-acylpyrrolidinium ions gave moderate to good yields of pyrrolo-tetrahydroisoquinolones and pyrrolo-benzazepinones respectively. Electron-donating R substituents enhanced the rate of reaction and gave higher yields than electron-withdrawing substituents. Substituents on the methyl or ethyl chain in general enhanced the reaction, unless sterically encumbered. The equivalent acylpiperidinium ions cyclised much

  三氟甲磺酸介导的N-芳基甲基-和N-芳基乙基-酰基吡咯烷鎓离子的环化分别给出了中等至良好的吡咯并四氢异喹啉酮和吡咯并苯并b庚酮的产率。供电子的R取代基比吸电子的取代基提高了反应速率并提供了更高的产率。除非空间上阻碍，否则甲基或乙基链上的取代基通常会增强反应。等效的酰基哌啶鎓离子环化的速度慢得多，产率也低。
• MOELLER, KEVIN D.;WANG, PO W.;TARAZI, SHARIF;MARZABADI, MOHAMMAD R.;WONG,+, J. ORG. CHEM., 56,(1991) N, C. 1058-1067
  作者：MOELLER, KEVIN D.、WANG, PO W.、TARAZI, SHARIF、MARZABADI, MOHAMMAD R.、WONG,+

  DOI：——

  日期：——
• Anodic amide oxidations in the presence of electron-rich phenyl rings: evidence for an intramolecular electron-transfer mechanism
  作者：Kevin D. Moeller、Po W. Wang、Sharif Tarazi、Mohammad R. Marzabadi、Poh Lee Wong

  DOI：10.1021/jo00003a029

  日期：1991.2

  The anodic oxidations of amides in the presence of mono-, di-, and trialkoxyphenyl rings were examined. Although literature reduction potentials suggest that these oxidations would lead to either selective aromatic ring oxidation or mixtures, the chemoselectivity of the reactions was found to be dependent on the substitution pattern of the phenyl ring. For example, the anodic oxidations of ((3-methoxyphenyl)acetyl)pyrrolidine, ((2-methoxyphenyl)acetyl)pyrrolidine, ((3-methoxy-4-(pivaloyloxy)phenyl)acetyl)pyrrolidine, and ((3,5-dimethoxy-4-(pivaloyloxy)phenyl)acetyl)pyrrolidine all led to selective methoxylation of the pyrrolidine ring. The anodic oxidations of ((4-methoxyphenyl)acetyl)pyrrolidine and ((3,4-methoxyphenyl)acetyl)pyrrolidine led to selective methoxylation of the benzylic carbon. Mechanistic studies indicate that both amide and aryl oxidation processes compete under the reaction conditions, but that intramolecular electron transfer leads to the selective formation of products. Evidence for this mechanism was obtained by examining the cyclic voltammogram of ((3-methoxyphenyl)-acetyl)pyrrolidine, competition studies, and the preparative electrolysis of ((4-methoxyphenyl)dimethyl-acetyl)pyrrolidine. The methoxylated amides were cyclized to form tricyclic amides using titanium tetrachloride.