(-)-14β-hydroxyvincadifformine | 62414-79-3

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 冬青素型生物碱
• 英文名称: (-)-14β-hydroxyvincadifformine
• 英文别名: methyl (1R,12R,14S,19S)-12-ethyl-14-hydroxy-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9-tetraene-10-carboxylate
• CAS: 62414-79-3
• 化学式: C₂₁H₂₆N₂O₃
• 分子量: 354.449
• InChiKey: OSFGKPUJCBBLSZ-CUCDBKBVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  61.8
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-14β-hydroxyvincadifformine 在 bicarbonate 、 间氯过氧苯甲酸 、 三苯基膦 作用下， 以 四氯化碳 、 二氯甲烷 、 乙腈 为溶剂， 反应 1.03h， 生成 (3aR,4R,5S,10bR,12bR)-3a-Ethyl-4,5-dihydroxy-3a,4,5,11,12,12b-hexahydro-1H-6,12a-diaza-indeno[7,1-cd]fluorene-5-carboxylic acid methyl ester
  参考文献：
  名称：

  Biomimetic alkaloid syntheses. 15. Enantioselective syntheses with epichlorohydrin: total syntheses of (+)-, (-)- and (.+-.)-vindoline and a synthesis of (-)-vindorosine

  摘要：

  DOI：

  10.1021/jo00379a006
• 作为产物：
  描述：

  methyl (2S,3aR,3a1S,10bR)-2-((tert-butyldimethylsilyl)oxy)-3a-ethyl-2,3,3a,3a1,4,6,11,12-octahydro-1H-indolizino[8,1-cd]carbazole-5-carboxylate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以73%的产率得到(-)-14β-hydroxyvincadifformine
  参考文献：
  名称：

  定向费歇尔吲哚化作为（+）-天冬酰胺和（-）-塔布罗宁的总合成方法

  摘要：

  开发了一种概念上新颖的合成方法，该方法可提供对蛇形精子生物碱（+）-aspidospermidine和（-）-tabersonine的一般使用途径。该方法基于烯-酰肼的区域选择性吲哚化，这是通过碱催化的分子内氮杂-Michael反应，原位捕获所得的烯醇化物以及随后的CN–N与酰肼的偶联而获得的。

  DOI：

  10.1021/acs.orglett.7b03078

文献信息

• Efficient total syntheses of (±)-vincadifformine and (−)-tabersonine
  作者：Satoshi Kobayashi、Ge Peng、Tohru Fukuyama

  DOI：10.1016/s0040-4039(98)02667-7

  日期：1999.2

  Stereocontrolled biomimetic total syntheses of the title compounds are described. Our syntheses feature a highly efficient preparation of the key intermediate 11 using our novel indole synthesis methodology. A novel amine protecting protocol by means of 2,4-dinitrobenzenesulfonamides has been developed to ensure the formation of the elusive secodine (3) as well as secodine-type intermediate (4) under

  描述了标题化合物的立体控制仿生全合成。我们的合成方法是使用我们新颖的吲哚合成方法高效制备关键中间体11。已经开发了借助于2，4-二硝基苯磺酰胺的新颖的胺保护方案，以确保在非常温和的条件下形成难以捉摸的苏木定（3）以及苏木定型中间体（4）。
• Synthesis of 18-Hydroxyvincamines and Epoxy-1,14-secovincamines; a New Proof for the Aspidospermane-Eburnane Rearrangement
  作者：András Nemes、Csaba Szántay、László Czibula、István Greiner

  DOI：10.3987/com-07-11114

  日期：——

  Chemical transformations started from tabersonine were studied. A one-pot oxidative ring-transformation with permaleic acid in methanol yielded 17,18-dehydrovincamine. Hydroboration-oxidation of the latter compound led to alkaloid 17,18-dehydrovincamone. Hydroboration-oxidation of tabersonine resulted 14 beta-hydroxyvineadifformine and 15p-hydroxyvincadifforinine. Allowing 14 beta- and 15 beta- hydroxyvincadifformines to react with permaleic acid/methanol provided 1,14-secovincamines, serving as new evidence for the mechanism of the aspidospermane-eburnane transformation. On the other hand 18 beta-hydroxyvincamine was obtained from 14 beta-hydroxyvincadifformine by reaction with 3-chloroperbenzoic acid and successive treatment with triphenylphosphine/aqueous acetic acid.
• Direct bromination or hydroxylation at C-11 in vincadifformine and tabersonine derivatives in superacids
  作者：C. Berrier、J.C. Jacquesy、M.P. Jouannetaud、Y. Vidal

  DOI：10.1016/s0040-4020(01)81365-x

  日期：1990.1
• Biomimetic alkaloid syntheses. 15. Enantioselective syntheses with epichlorohydrin: total syntheses of (+)-, (-)- and (.+-.)-vindoline and a synthesis of (-)-vindorosine
  作者：Martin E. Kuehne、David E. Podhorez、Tshilundu Mulamba、William G. Bornmann

  DOI：10.1021/jo00379a006

  日期：1987.2
• Directed Fischer Indolization as an Approach to the Total Syntheses of (+)-Aspidospermidine and (−)-Tabersonine
  作者：Joo-Young Kim、Chang-Heon Suhl、Joon-Ho Lee、Cheon-Gyu Cho

  DOI：10.1021/acs.orglett.7b03078

  日期：2017.11.17

  A conceptually new synthetic approach that provides general access to the aspidosperma alkaloids (+)-aspidospermidine and (−)-tabersonine was developed. This method is based on the regioselective indolization of an ene–hydrazide, which was obtained via a base-catalyzed intramolecular aza-Michael reaction, in situ trapping of the resulting enolate, and subsequent C–N coupling with phenyl hydrazide.

  开发了一种概念上新颖的合成方法，该方法可提供对蛇形精子生物碱（+）-aspidospermidine和（-）-tabersonine的一般使用途径。该方法基于烯-酰肼的区域选择性吲哚化，这是通过碱催化的分子内氮杂-Michael反应，原位捕获所得的烯醇化物以及随后的CN–N与酰肼的偶联而获得的。