protoverbine | 216855-63-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: protoverbine
• 英文别名: (-)-(S)-protoverbine；(8S)-8-phenyl-1,5,9,13-tetrazacycloheptadecan-6-one
• CAS: 216855-63-9
• 化学式: C₁₉H₃₂N₄O
• 分子量: 332.489
• InChiKey: XLQJYFZMKKAAMB-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  65.2
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  protoverbine 在 三乙胺 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 (+)-(S)-verbamekrine
  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
• 作为产物：
  描述：

  (+)-(2S)-2-phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one 在 盐酸 、 羟胺 作用下， 以 水 为溶剂， 生成 protoverbine
  参考文献：
  名称：

  Chiroptical Properties of the Protoverbine Class of Macrocyclic Spermine Alkaloids

  摘要：

  The chiroptical properties (circular dichroism, CD) of the 17-membered macrocyclic spermine lactam alkaloids (-)-protoverbine (16), its N,N'-methylene-bridged natural analogue (+)-protomethine (17), their natural derivatives (-)-verbacine (1), (-)-verballocine (2), (-)-verbascenine (3), (-)-verballoscenine (4), (+) verbamethine (5), (+)-incasine C (6), (+)-verdoline (incasine B', 30), (+)-incasine B (31), and some of their isosteric analogues were studied. By chemical and chiroptical correlation, it was confirmed that an amidically bonded (S)-beta-phenyl-beta-alanine fragment forms the chiral moiety in all of these natural compounds The signs of the registered Cotton effects (CEs) are interpreted in terms of the Smith's quadrant rule for the L-1(b) CEs of chiral a-substituted benzylamines and the Ogura's sign rule for n --> pi* CEs of lactams. Some of the conclusions regarding configuration are supported for the rigid bicyclic compound (-)-(9S)-9-phenyl-1,6-diazabicyclo[4.3.1]decan-7-one (15) by the X-ray crystal structure of the racemate.

  DOI：

  10.1002/(sici)1522-2675(19981007)81:10<1773::aid-hlca1773>3.0.co;2-x

文献信息

• 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.
• Chiroptical Properties of the Protoverbine Class of Macrocyclic Spermine Alkaloids
  作者：Konstantin Drandarov、Armin Guggisberg、Anthony Linden、Manfred Hesse

  DOI：10.1002/(sici)1522-2675(19981007)81:10<1773::aid-hlca1773>3.0.co;2-x

  日期：1998.10.7

  The chiroptical properties (circular dichroism, CD) of the 17-membered macrocyclic spermine lactam alkaloids (-)-protoverbine (16), its N,N'-methylene-bridged natural analogue (+)-protomethine (17), their natural derivatives (-)-verbacine (1), (-)-verballocine (2), (-)-verbascenine (3), (-)-verballoscenine (4), (+) verbamethine (5), (+)-incasine C (6), (+)-verdoline (incasine B', 30), (+)-incasine B (31), and some of their isosteric analogues were studied. By chemical and chiroptical correlation, it was confirmed that an amidically bonded (S)-beta-phenyl-beta-alanine fragment forms the chiral moiety in all of these natural compounds The signs of the registered Cotton effects (CEs) are interpreted in terms of the Smith's quadrant rule for the L-1(b) CEs of chiral a-substituted benzylamines and the Ogura's sign rule for n --> pi* CEs of lactams. Some of the conclusions regarding configuration are supported for the rigid bicyclic compound (-)-(9S)-9-phenyl-1,6-diazabicyclo[4.3.1]decan-7-one (15) by the X-ray crystal structure of the racemate.