(S)-1-<(5-methoxy-1,4-cyclohexadienyl)methyl>-1,2,3,4-tetrahydroisoquinoline | 136587-48-9

• 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: (S)-1-<(5-methoxy-1,4-cyclohexadienyl)methyl>-1,2,3,4-tetrahydroisoquinoline
• 英文别名: (S)-1-[(5-methoxy-1,4-cyclohexadienyl)methyl]-1,2,3,4-tetrahydroisoquinoline；(1S)-6,7-dimethoxy-1-[(5-methoxycyclohexa-1,4-dien-1-yl)methyl]-1,2,3,4-tetrahydroisoquinoline
• CAS: 136587-48-9
• 化学式: C₁₉H₂₅NO₃
• 分子量: 315.412
• InChiKey: HULDQPCWZJKPAY-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  39.7
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-1-<(5-methoxy-1,4-cyclohexadienyl)methyl>-1,2,3,4-tetrahydroisoquinoline 在 水 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 溶剂黄146 为溶剂， 反应 29.25h， 生成 (8aS,12aS,13aS)-2,3,12a-trimethoxy-5,6,8,8a,9,10,11,12,13,13a-decahydroisoquinolino[2,1-b]isoquinolin-11-ol
  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：

  (S)-(-)-(3-methoxybenzyl)-1,2,3,4-tetrahydroisoquinoline 在 氨 、 sodium 、 叔丁醇 作用下， 以98%的产率得到(S)-1-<(5-methoxy-1,4-cyclohexadienyl)methyl>-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

文献信息

• 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.