(19E)-cur-19-ene-17,18-diol | 900-98-1

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 马钱子生物碱
• 英文名称: (19E)-cur-19-ene-17,18-diol
• 英文别名: (19E)-Cur-19-en-17,18-diol；(2E)-2-[(1S,9S,10R,11R,17S)-10-(hydroxymethyl)-8,14-diazapentacyclo[9.5.2.01,9.02,7.014,17]octadeca-2,4,6-trien-12-ylidene]ethanol
• CAS: 900-98-1
• 化学式: C₁₉H₂₄N₂O₂
• 分子量: 312.412
• InChiKey: TWZXGHUORNLMGZ-DYAJAIQSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  55.7
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (19E)-cur-19-ene-17,18-diol 生成 tetrahydronorfluorocurarine
  参考文献：
  名称：

  关于Calebassen生物碱C-Dihydrotoxiferin和C-Toxiferin-I以及Strychnos toxifera的生物碱Caracurin-V的组成。以WIELAND-GUMLICH醛为原料的合成实验。36.关于Calebasse生物碱的交流

  摘要：

  目前的工作表示说明书和我们最近发表的初步通信的扩展16上C-二氢toxiferin和半二氢toxiferin和相关化合物的相互转化）。

  DOI：

  10.1002/hlca.19580410741
• 作为产物：
  描述：

  5-(2-(1-((1R,3R,5R)-3-((E)-4-(tert-butoxy)-1-chlorobut-2-en-2-yl)-6-oxabicyclo[3.1.0]hexan-1-yl)vinyl)phenyl)-1,3-dimethyl-1,3,5-triazinan-2-one 在 盐酸 、 氢氧化钾 、 硫酸 、 sodium hydride 、 二异丁基氢化铝 、 sodium sulfate 、 锌 、 lithium diisopropyl amide 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 、 乙腈 、 苯 为溶剂， 反应 78.92h， 生成 (19E)-cur-19-ene-17,18-diol
  参考文献：
  名称：

  Asymmetric Total Syntheses of (-)- and (+)-Strychnine and the Wieland-Gumlich Aldehyde

  摘要：

  The first asymmetric total syntheses of (-)-strychnine, ent-strychnine, and the Wieland-Gumlich aldehyde are described with full experimental details. The total synthesis of (-)-strychnine was realized in 24 steps and 3% overall yield from (1R,4S)-(+)-4-hydroxy-2-cyclopentenyl acetate (28). This synthesis fully controls the six stereogenic centers and forms the C(20) double bond of (-)-strychnine with high diastereoselection (>20:1). In the first stage of the synthesis, the (R)-cyclopentenylstannane 8 is prepared in nine steps and 30% overall yield (40% with one recycle of 38) as summarized in Scheme 4. Palladium-catalyzed carbonylative coupling of 8 with the 2-iodoaniline derivative 7 provides enone 6, which is converted to the 2-azabicyclo[3.2.1]octane 5 in seven additional steps. This latter sequence proceeds in 36% overall yield (Scheme 6). The central step of the total synthesis is aza-Cope-Mannich rearrangement of 5 which proceeds in 98% yield to form the pentacyclic intermediate 4 (Scheme 7). In five additional steps 4 is converted to the Wieland-Gumlich aldehyde 2, which is the ultimate precursor of (-)strychnine. A slight modification of this synthesis strategy allowed ent-strychnine to be prepared and provided the first samples of this unnatural enantiomer for pharmacological studies (Scheme 8). The efficiency and conciseness of this synthesis provide an important benchmark of the power of the aza-Cope rearrangement-Mannich reaction to solve formidable problems in alkaloid construction.

  DOI：

  10.1021/ja00126a017

文献信息

• Further alkaloids from strychnos longicaudata and strychnos ngouniensis
  作者：Georges Massiot、Philippe Thépenier、Marie-José Jacquier、Joseph Lounkokobi、Catherine Mirand、Monique Zèches、Louisette Le Men-Olivier、Clément Delaude

  DOI：10.1016/s0040-4020(01)88603-8

  日期：1983.1

  Twenty four alkaloids have been isolated and identified from the root and stem barks of Strychnos longicaudata Gilg and Strychnos ngouniensis Pellegrin. Among these, 17 alkaloids are isolated for the first time; the novel bisindole series represented by longicaudatine includes now two other compounds: longicaudatines F and Y; besides ngouniensine, its epimer epingouniensine has been isolated along

  二十四生物碱已被隔离并从根本上确定和茎的皮制马钱子longicaudata白木香和马钱子ngouniensis佩列格林。其中，首次分离出17种生物碱。以龙胆碱所代表的新型双吲哚系列现在还包括另外两种化合物：龙胆碱F和Y。除了恩古尼碱以外，它的差向异构体恩尼古丁碱还与两个葡糖基-恩尼古丁碱一起被分离出来。其他新的生物碱包括肾小管肾上腺素和几个具有akuammicine骨架的碱基。
• Alkaloids of Australian Strychnos species. Part II. The constitution of strychnospermine and spermostrychnine
  作者：F. A. L. Anet、Robert Robinson

  DOI：10.1039/jr9550002253

  日期：——
• Fritz et al., Justus Liebigs Annalen der Chemie, 1963, vol. 663, p. 150,155
  作者：Fritz et al.

  DOI：——

  日期：——
• Carbon-13 nuclear magnetic resonance spectroscopy of naturally occurring substances. 56. Strychnos alkaloids
  作者：Ernest Wenkert、H. T. Andrew Cheung、Hugo E. Gottlieb、Michel C. Koch、Alain Rabaron、Michel M. Plat

  DOI：10.1021/jo00400a017

  日期：1978.3
• Asymmetric Total Syntheses of (-)- and (+)-Strychnine and the Wieland-Gumlich Aldehyde
  作者：Steven D. Knight、Larry E. Overman、Garry Pairaudeau

  DOI：10.1021/ja00126a017

  日期：1995.5

  The first asymmetric total syntheses of (-)-strychnine, ent-strychnine, and the Wieland-Gumlich aldehyde are described with full experimental details. The total synthesis of (-)-strychnine was realized in 24 steps and 3% overall yield from (1R,4S)-(+)-4-hydroxy-2-cyclopentenyl acetate (28). This synthesis fully controls the six stereogenic centers and forms the C(20) double bond of (-)-strychnine with high diastereoselection (>20:1). In the first stage of the synthesis, the (R)-cyclopentenylstannane 8 is prepared in nine steps and 30% overall yield (40% with one recycle of 38) as summarized in Scheme 4. Palladium-catalyzed carbonylative coupling of 8 with the 2-iodoaniline derivative 7 provides enone 6, which is converted to the 2-azabicyclo[3.2.1]octane 5 in seven additional steps. This latter sequence proceeds in 36% overall yield (Scheme 6). The central step of the total synthesis is aza-Cope-Mannich rearrangement of 5 which proceeds in 98% yield to form the pentacyclic intermediate 4 (Scheme 7). In five additional steps 4 is converted to the Wieland-Gumlich aldehyde 2, which is the ultimate precursor of (-)strychnine. A slight modification of this synthesis strategy allowed ent-strychnine to be prepared and provided the first samples of this unnatural enantiomer for pharmacological studies (Scheme 8). The efficiency and conciseness of this synthesis provide an important benchmark of the power of the aza-Cope rearrangement-Mannich reaction to solve formidable problems in alkaloid construction.