(-)-(S)-8-(4-methoxyphenyl)-1,5,9,13-tetraazacycloheptadecan-6-one | 151813-62-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: (-)-(S)-8-(4-methoxyphenyl)-1,5,9,13-tetraazacycloheptadecan-6-one
• 英文别名: (-)-(S)-buchnerine；(S)-buchnerine；(8S)-8-(4-methoxyphenyl)-1,5,9,13-tetrazacycloheptadecan-6-one
• CAS: 151813-62-6
• 化学式: C₂₀H₃₄N₄O₂
• 分子量: 362.516
• InChiKey: YMAWLWVKJGYXTR-IBGZPJMESA-N

物化性质

• 沸点：
  583.2±50.0 °C(Predicted)
• 密度：
  0.978±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  74.4
• 氢给体数：
  4
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-(S)-8-(4-methoxyphenyl)-1,5,9,13-tetraazacycloheptadecan-6-one 在 盐酸羟胺 、 2-氯-1-甲基吡啶碘化物 作用下， 以 盐酸 、 甲醇 、 二氯甲烷 、 水 、 三乙胺 为溶剂， 反应 17.0h， 生成 (-)-(8S)-1-[(E)-3-(4-methoxyphenyl)prop-2-enoyl]-8-(4-methoxyphenyl)-1,5,9,13-tetraazacycloheptadecan-6-one
  参考文献：
  名称：

  [D8]-标记的 (-)-(S)-二羟基白藜芦醇的不对称合成，大双环精胺生物碱 Aphelandrine 和 Orantine 生物发生中的末端前体

  摘要：

  未标记和 [D8] 标记的末端前体 4 ((-)-(S)-dihydroxyverbacine) 和 19 分别在精胺生物碱 aphelandrine (5) 和 orantine (6) 的生物发生中的不对称合成，分别, 被描述。还介绍了生物碱 (-)-(S)-[(E)-4-methoxycinnamoyl]buchnerine (10) 的部分合成。

  DOI：

  10.1002/1522-2675(20001108)83:11<2953::aid-hlca2953>3.0.co;2-i
• 作为产物：
  描述：

  methyl (+)-(3S)-3-amino-3-(4-methoxyphenyl)propanoate 在 copper diacetate caesium carbonate 、 三乙胺 作用下， 以 氯仿 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 28.5h， 生成 (-)-(S)-8-(4-methoxyphenyl)-1,5,9,13-tetraazacycloheptadecan-6-one
  参考文献：
  名称：

  Asymmetric Syntheses of the Macrocyclic Spermine Alkaloids (−)-(S)-Protoverbine, (−)-(S)-Buchnerine, and Their Naturally Occurring Congenial Alkaloids

  摘要：

  Asymmetric syntheses of the following 17-membered macrocyclic spermine alkaloids are presented: (-)-(S)-protoverbine (= (8S)-8-phenyl-1,5,9,13-tetraazacycloheptadecane-6-one; 1), (+)-(S)-protomethine (=(2S)-2-phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one; 2), (-)-(S)-buchnerine (=(8S)-8-(4-methoxyphenyl)-1,5,9,13-tetraazacycloheptadecane-6-one; 8), (+)-(S)-VeTbamethine (=(-')-(2S)-9-[(E)-phenylprop- 2-enoyl]-2-phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one; 4), (-)-(S)-verbacine [(E)-phenylprop-2-enoyl]-8-phenyl-1,5,9,13-tetraazacycloheptadecan-6-one; 3), (-)-(S)-verbasikrine (8S)-1-[(E)-3-(4-methoxyphenyl)prop-2-enoyl]-8-phenyl-1,5,9,13-tetraazacycloheptadecan-6-one; 26), (S)-isoverbasikrine (=(-)-(8S)-1-[(Z)-3-(4-methoxyphenyl)prop-2-enoyl]-8-phenyl-1,5,9,13-tetraazacycloheptadecan-6-one; 25), (+)-(S)-verbamekrine (= (+)-(2S)-9-[(E)-3-(4-methoxyphenyl)prop-2-enoyl]-2-phenyl- 1,5,9.14-tetraazabicyclo[12.3.1]octadecan-4- one; 23), and(+)-(S)-isoverbamekrine (=(+)-(2S)-9-[(Z)-3-(4-methoxyphenyl)prop-2-enoyl]-2-phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one; 24). Effective methods for H-1-NMR determination of the enantiomeric purity in which (S)-2-hydroxy-2-phenylacetic acid and (S)-2-acetoxy-2-phenylacetic acid are used as shift reagents for 1, 8, and related macrocyclic alkaloids are described.

  DOI：

  10.1002/1522-2675(200204)85:4<979::aid-hlca979>3.0.co;2-f

文献信息

• Biomimetic Formation of Macrocyclic Spermine Alkaloids
  作者：Vladimir Dimitrov、Hervé Geneste、Armin Guggisberg、Manfred Hesse

  DOI：10.1002/1522-2675(20010711)84:7<2108::aid-hlca2108>3.0.co;2-g

  日期：2001.7.11

  Dihydroxyverbacine (10), a precursor for oxidative phenol coupling. was obtained via (+/-)-buchnerine (14). whose synthesis is described. The oxidizing system hemin (ferriprotoporphyrin IX chloride)/H2O2 promoted intramolecular coupling of 10 to give the alkaloids aphelandrine (1). orantine (2), and chaenorpine (7). The alkaloids were identified by on-line coupled HPLC and atmospheric-pressure chemical-ionization (APCI) mass spectrometry.
• Prelandrine, the Key-Step Intermediate in the Biosynthesis of the Macrocyclic Spermine Alkaloid Aphelandrine
  作者：Lenka Nezbedová、Manfred Hesse、Konstantin Drandarov、Christa Werner

  DOI：10.1002/1522-2675(20010131)84:1<172::aid-hlca172>3.0.co;2-b

  日期：2001.1.31

  By means of the high sensitive on-line-coupled high-performance liquid chromatography and atmospheric-pressure chemical-ionization mass spectrometry (HPLC/APCI-MS and HPLC/APCI-MS/MS) techniques, the new macrocyclic spermine alkaloid prelandrine (5) was detected in the roots of Aphelandra squarrosa (Acanthaceae), and its structure was elucidated as 4'-hydroxyprotoverbine (=8-(4-hydroxyphenyl)-1,5,9,13-tetraazacycloheptadecan-6-one). It was further demonstrated that protoverbine (6) is enzymatically hydroxylated to prelandrine (5) in a reaction catalyzed by microsomes from the roots of A. squarrosa. The chemical synthesis of (-)-(S)-prelandrine is also described. The possible key role of prelandrine (5) as an intermediate in the biosynthesis of aphelandrine (1) is discussed.
• Asymmetric Syntheses of the Macrocyclic Spermine Alkaloids (−)-(S)-Protoverbine, (−)-(S)-Buchnerine, and Their Naturally Occurring Congenial Alkaloids
  作者：Konstantin Drandarov、Armin Guggisberg、Manfred Hesse

  DOI：10.1002/1522-2675(200204)85:4<979::aid-hlca979>3.0.co;2-f

  日期：2002.4

  Asymmetric syntheses of the following 17-membered macrocyclic spermine alkaloids are presented: (-)-(S)-protoverbine (= (8S)-8-phenyl-1,5,9,13-tetraazacycloheptadecane-6-one; 1), (+)-(S)-protomethine (=(2S)-2-phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one; 2), (-)-(S)-buchnerine (=(8S)-8-(4-methoxyphenyl)-1,5,9,13-tetraazacycloheptadecane-6-one; 8), (+)-(S)-VeTbamethine (=(-')-(2S)-9-[(E)-phenylprop- 2-enoyl]-2-phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one; 4), (-)-(S)-verbacine [(E)-phenylprop-2-enoyl]-8-phenyl-1,5,9,13-tetraazacycloheptadecan-6-one; 3), (-)-(S)-verbasikrine (8S)-1-[(E)-3-(4-methoxyphenyl)prop-2-enoyl]-8-phenyl-1,5,9,13-tetraazacycloheptadecan-6-one; 26), (S)-isoverbasikrine (=(-)-(8S)-1-[(Z)-3-(4-methoxyphenyl)prop-2-enoyl]-8-phenyl-1,5,9,13-tetraazacycloheptadecan-6-one; 25), (+)-(S)-verbamekrine (= (+)-(2S)-9-[(E)-3-(4-methoxyphenyl)prop-2-enoyl]-2-phenyl- 1,5,9.14-tetraazabicyclo[12.3.1]octadecan-4- one; 23), and(+)-(S)-isoverbamekrine (=(+)-(2S)-9-[(Z)-3-(4-methoxyphenyl)prop-2-enoyl]-2-phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one; 24). Effective methods for H-1-NMR determination of the enantiomeric purity in which (S)-2-hydroxy-2-phenylacetic acid and (S)-2-acetoxy-2-phenylacetic acid are used as shift reagents for 1, 8, and related macrocyclic alkaloids are described.
• The Asymmetric Synthesis of the [D8]-Labeled (−)-(S)-Dihydroxyverbacine, the Terminal Precursor in the Biogenesis of the Macrobicyclic Spermine Alkaloids Aphelandrine and Orantine
  作者：Lenka Nezbedová、Konstantin Drandarov、Christa Werner、Manfred Hesse

  DOI：10.1002/1522-2675(20001108)83:11<2953::aid-hlca2953>3.0.co;2-i

  日期：2000.11.8

  The asymmetric synthesis of the unlabeled and [D8]-labeled terminal precursors, 4 ((−)-(S)-dihydroxyverbacine) and 19, respectively, in the biogenesis of the spermine alkaloids aphelandrine (5) and orantine (6), respectively, is described. A partial synthesis of the alkaloid (−)-(S)-[(E)-4-methoxycinnamoyl]buchnerine (10) is also presented.

  未标记和 [D8] 标记的末端前体 4 ((-)-(S)-dihydroxyverbacine) 和 19 分别在精胺生物碱 aphelandrine (5) 和 orantine (6) 的生物发生中的不对称合成，分别, 被描述。还介绍了生物碱 (-)-(S)-[(E)-4-methoxycinnamoyl]buchnerine (10) 的部分合成。