(-)-limaspermidine | 72821-58-0

• 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: (-)-limaspermidine
• 英文别名: 2-[(1S,9S,12S,19S)-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6-trien-12-yl]ethanol
• CAS: 72821-58-0
• 化学式: C₁₉H₂₆N₂O
• 分子量: 298.428
• InChiKey: XSMCTYIPFHFOEM-VJANTYMQSA-N

物化性质

• 熔点：
  227-228 °C
• 沸点：
  469.8±38.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  35.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-limaspermidine 在 mercury(II) diacetate 、 溶剂黄146 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 17.0h， 生成 1-Acetyl-aspidoalbidin
  参考文献：
  名称：

  Application of a Raney-Cobalt-Mediated Tandem Reductive Cyclization Protocol to Total Syntheses of the Aspidosperma Alkaloids (±)-Limaspermidine and (±)-1-Acetylaspidoalbidine

  摘要：

  The racemic modification of the Aspidosperma alkaloid limaspermidine (1) has been prepared in ten steps including one involving a Raneycobalt-mediated tandem reductive cyclization of nitrile 8 to give the tetracyclic system 9b. Compound (+/-)-1 has been converted over two steps into (+/-)-1-acetylaspidoalbidine [(+/-)-13].

  DOI：

  10.1021/ol3026846
• 作为产物：
  描述：

  6aα-<2-(benzyloxy)ethyl>-8aα-<1-(2-aminophenyl)ethenyl>-1,2,4,6a,7,8,8a,8bα-octahydro-1-oxacyclopentindolizine 在 palladium on activated charcoal lithium aluminium tetrahydride 、 camphor-10-sulfonic acid 、 氨 、 甲酸铵 、 sodium 、 sodium sulfate 作用下， 以 四氢呋喃 、 乙醇 、 苯 为溶剂， 反应 5.5h， 生成 (-)-limaspermidine
  参考文献：
  名称：

  Overmann, Larry E.; Robertson, Graeme M.; Robichaud, Albert J., Journal of the American Chemical Society, 1991, vol. 113, # 7, p. 2598 - 2610

  摘要：

  DOI：

文献信息

• Enantioselective Total Synthesis of (−)-Limaspermidine and Formal Synthesis of (−)-1-Acetylaspidoalbidine
  作者：Shao-Xiong Zhang、Xiao-Lei Shen、Ze-Qian Li、Li-Wei Zou、Feng-Qun Wang、Hong-Bin Zhang、Zhi-Hui Shao

  DOI：10.1021/jo402004f

  日期：2013.11.15

  culminated in the first asymmetric total synthesis of the Aspidosperma alkaloid limaspermidine is described. The successful enantioselective route to (−)-limaspermidine proceeds in 10 steps and with the isolation of only six intermediates using a Pd-catalyzed enantioselective decarboxylative allylation we have recently developed. This first enantioselective synthesis of (−)-limaspermidine establishes

  描述了合成策略的演变，该策略最终导致了Asperdosperma生物碱Limaspermidine的首次不对称全合成。我们最近开发了成功的对（-）-利马斯idine定的对映选择性路线，该路线分10个步骤进行，仅使用Pd催化的对映选择性脱羧烯丙基化仅分离六个中间体即可。（-）-利马培啶的该第一对映选择性合成明确地建立了其绝对构型，并允许Aspidoalbine生物碱（-）-1-乙酰基aspidobidine的第一不对称形式的全合成。
• Enantioselective Total Synthesis of (−)‐Limaspermidine and (−)‐Kopsinine by a Nitroaryl Transfer Cascade Strategy
  作者：Brendan Horst、Daniël S. Verdoorn、Sven Hennig、Gydo van der Heijden、Eelco Ruijter

  DOI：10.1002/anie.202210592

  日期：2022.10.17

  protective groups by their use in a long-range nitroarene transfer cascade reaction. Using a suitably functionalized precursor, this process was used as the key step in the enantioselective total synthesis of the monoterpene indole alkaloids (−)-limaspermidine, (−)-kopsinilam, and (−)-kopsinine as well as the unnatural alkaloid (−)-tetra-hydrokopsifoline D.

  2-硝基苯磺酰胺可通过在长程硝基芳烃转移级联反应中用作功能性保护基团。使用适当功能化的前体，该过程被用作单萜吲哚生物碱 (−)-limaspermidine、(−)-kopsinilam 和 (−)-kopsinine 以及非天然生物碱 (−)-kopsinine 的对映选择性全合成的关键步骤。 )-四氢科西林 D.
• Total Syntheses of Dihydroindole <i>Aspidosperma</i> Alkaloids: Reductive Interrupted Fischer Indolization Followed by Redox Diversification
  作者：Gábor Martin、Péter Angyal、Orsolya Egyed、Szilárd Varga、Tibor Soós

  DOI：10.1021/acs.orglett.0c01472

  日期：2020.6.19

  We report a novel reductive interrupted Fischer indolization process for the concise assembly of the 20-oxoaspidospermidine framework. This rapid complexity generating route paves the way toward various dihydroindole Aspidosperma alkaloids with different C-5 side chain redox patterns. The end-game redox modulations were accomplished by modified Wolff–Kishner reaction and photo-Wolff rearrangement,

  我们报告了一个新颖的还原性中断费休吲哚化过程为20-oxoaspidospermidine框架的简洁组装。这种快速的复杂性生成途径为各种具有不同C-5侧链氧化还原模式的二氢吲哚曲霉生物碱铺平了道路。最终的氧化还原调节通过改良的Wolff-Kishner反应和光-沃尔夫重排完成，从而可以合成（-）-aspidospermidine，（-）-limaspermidine和（+）-17- demethoxy- N - acetylcylindrocarine和（-）-1-乙酰基aspidobidine的正式全合成。
• Total Synthesis of (±)-Aspidospermidine, (±)-Aspidofractinine, (±)-Limaspermidine, and (±)-Vincadifformine via a Cascade and Common Intermediate Strategy
  作者：David L. Cain、Niall A. Anderson、David B. Cordes、Alexandra M. Z. Slawin、Allan J. B. Watson

  DOI：10.1021/acs.joc.2c02099

  日期：2022.11.18

  A concise strategy for the total synthesis of several Aspidosperma alkaloids is reported. A Suzuki–Miyaura cross-coupling provides access to a 2-vinyl indole that undergoes a Diels–Alder cascade reaction with butyn-2-one to deliver a pyrroloindoline intermediate. This undergoes cascade amidation, reduction, skeletal rearrangement, and intramolecular Michael addition to provide a common intermediate

  报道了几种Aspidosperma生物碱的全合成简明策略。Suzuki–Miyaura 交叉偶联提供了获得 2-乙烯基吲哚的途径，该吲哚与 b​​utyn-2-one 发生 Diels-Alder 级联反应以提供吡咯并二氢吲哚中间体。这经历了级联酰胺化、还原、骨架重排和分子内迈克尔加成，以提供包含Aspidosperma生物碱完整框架的常见中间体。该中间体的效用体现在四种不同天然产物的合成中。
• Development of a Strategy for the Total Synthesis of <i>Aspidosperma</i> Alkaloids via the Cyclobutenone-Based PET-Initiated Cationic Radical-Driven [2+2]/Retro-Mannich Reaction
  作者：Jianyu Long、Rudong Liu、Xinpeng Mu、Zhilin Song、Zhongchao Zhang、Zhen Yang

  DOI：10.1021/acs.orglett.4c00540

  日期：2024.4.19

  A novel strategy for the synthesis of Aspidosperma alkaloids has been achieved via a photoredox-initiated [2+2]/retro-Mannich reaction of tryptamine-substituted enaminones as a key step. The developed chemistry has been applied to the construction of the core tetracycle of Aspidosperma alkaloids (±)-aspidospermidine and (±)-limaspermidine.

  通过色胺取代的烯胺酮的光氧化还原引发的[2+2]/逆曼尼希反应作为关键步骤，实现了一种合成Aspidosperma生物碱的新策略。所开发的化学方法已应用于Aspidosperma生物碱 (±)-aspidospermidine 和 (±)-limaspermidine 核心四环的构建。