1-<(3,5-dioxahex-1-enyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline | 136587-56-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: 1-<(3,5-dioxahex-1-enyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
• 英文别名: 1-[(3,5-dioxahex-1-enyl)methyl]-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline；(1S)-6,7-dimethoxy-1-[2-(methoxymethoxy)prop-2-enyl]-1,2,3,4-tetrahydroisoquinoline
• CAS: 136587-56-9
• 化学式: C₁₆H₂₃NO₄
• 分子量: 293.363
• InChiKey: NTVUKMOGAQTYLD-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  49
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 1-<(3,5-dioxahex-1-enyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 在 camphor-10-sulfonic acid 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 (S)-9,10-dimethoxy-1,3,4,6,7,11b-hexahydro-2H-benzoquinolizin-2-one 、 (11bR)-9,10-dimethoxy-1,3,4,6,7,11b-hexahydrobenzo[a]quinolizin-2-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
• 作为产物：
  描述：

  2-(氯甲基)-3,5-二氧杂-1-己烯 、 ((S)-1-tert-Butoxymethyl-2-methyl-propyl)-[1-(6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-meth-(E)-ylidene]-amine 生成 1-<(3,5-dioxahex-1-enyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 、 1-<(3,5-dioxahex-1-enyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
  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