(S)-(-)-2,3-dimethoxy-5,6,8,8a,9,10,13,13a-octahydro-11H-dibenzoquinolizin-1-one | 136657-33-5

• 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: (S)-(-)-2,3-dimethoxy-5,6,8,8a,9,10,13,13a-octahydro-11H-dibenzoquinolizin-1-one
• 英文别名: 7,8-Dimethoxy-12,13-didehydroberban；(S)-(-)-2,3-dimethoxy-5,6,8,8a,9,10,13,13a-octahydro-11H-dibenzo[a,g]quinolizin-1-one；(8aR,13aS)-2,3-dimethoxy-5,6,8,8a,9,10,13,13a-octahydroisoquinolino[2,1-b]isoquinolin-11-one
• CAS: 136657-33-5
• 化学式: C₁₉H₂₃NO₃
• 分子量: 313.397
• InChiKey: KIJMJVNSLOIVHT-GUYCJALGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (S)-(-)-(3-methoxybenzyl)-1,2,3,4-tetrahydroisoquinoline 在 草酰氯 、 氨 、 水 、 sodium 、 sodium cyanoborohydride 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 、 叔丁醇 作用下， 以 溶剂黄146 为溶剂， 反应 29.67h， 生成 (S)-(-)-2,3-dimethoxy-5,6,8,8a,9,10,13,13a-octahydro-11H-dibenzoquinolizin-1-one
  参考文献：
  名称：

  Asymmetric synthesis of benzoquinolizidines: a formal synthesis of (-)-emetine

  摘要：

  Chiral formamidines affixed to tetrahydroisoquinoline derivatives affords the appropriate precursor 9 to various benzo[a]quinolizidines 2 and 3 and dibenzo[a,g]quinolizidines 4 in modest to high optical purity. Both 3 and 4 have been utilized in total syntheses of natural emetine 1, thus the route herein constitutes a formal total synthesis of 1. Furthermore, Mannich cyclizations of 1-alkylisoquinolines 18a-c proceeded with or without loss of absolute stereochemistry at the C-1 position. Explanation for this behavior is based upon whether a [3,3] rearrangement or a Mannich reaction takes place. The former results in virtually complete racemization of 18, whereas the latter totally conserves the chirality in 18. Finally, 1-alkynylisoquinolines of high optical purity were transformed, via the Overman protocol, to alkylidine benzo[a]quinolizidines 24 in good yield and to our knowledge, high enantiomeric excess.

  DOI：

  10.1021/jo00024a032

文献信息

• Conjugate Addition−Dipolar Cycloaddition Cascade for the Synthesis of Benzo[<i>a</i>]quinolizine and Indolo[<i>a</i>]quinolizine Scaffolds: Application to the Total Synthesis of (±)-Yohimbenone
  作者：Chad J. Stearman、Michael Wilson、Albert Padwa

  DOI：10.1021/jo9003579

  日期：2009.5.1

  A highly efficient total synthesis of (±)-yohimbenone and a formal synthesis of (±)-emetine is described. The key element of the synthesis consists of a conjugate addition−dipolar cycloaddition of 2,3-bis(phenylsulfonyl)-1,3-butadiene with an appropriate oxime. The resulting cycloadducts are cleaved reductively to provide azapolycyclic scaffolds with strategically placed functionality for further manipulation

  描述了高效的（±）-育亨宁酮的全合成和（±）-乙美汀的形式上的合成。合成的关键元素包括2,3-双（苯磺酰基）-1,3-丁二烯与适当的肟的共轭加成-偶极环加成。所得的环加合物被还原性裂解，以提供具有策略性放置的功能的氮杂多环支架，以进一步处理目标化合物。
• Asymmetric synthesis of benzoquinolizidines: a formal synthesis of (-)-emetine
  作者：Joseph W. Guiles、A. I. Meyers

  DOI：10.1021/jo00024a032

  日期：1991.11

  Chiral formamidines affixed to tetrahydroisoquinoline derivatives affords the appropriate precursor 9 to various benzo[a]quinolizidines 2 and 3 and dibenzo[a,g]quinolizidines 4 in modest to high optical purity. Both 3 and 4 have been utilized in total syntheses of natural emetine 1, thus the route herein constitutes a formal total synthesis of 1. Furthermore, Mannich cyclizations of 1-alkylisoquinolines 18a-c proceeded with or without loss of absolute stereochemistry at the C-1 position. Explanation for this behavior is based upon whether a [3,3] rearrangement or a Mannich reaction takes place. The former results in virtually complete racemization of 18, whereas the latter totally conserves the chirality in 18. Finally, 1-alkynylisoquinolines of high optical purity were transformed, via the Overman protocol, to alkylidine benzo[a]quinolizidines 24 in good yield and to our knowledge, high enantiomeric excess.