(+/-)-aspidofractinine

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 白坚木瑞亭生物碱
• 英文名称: (+/-)-aspidofractinine
• 化学式: C₁₉H₂₄N₂
• 分子量: 280.413
• InChiKey: BIBZWCCWSCCFBB-CADBVGFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  15.27
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  (+/-)-20-oxoaspidofractinine 在 肼 作用下， 以74%的产率得到(+/-)-aspidofractinine
  参考文献：
  名称：

  APPLICATION OF THE NEW ACYLATING AGENTS [PhS(O)–CH=C(OMe)Cl AND PhSO₂–CH=C(OMe)Cl] TO THE SYNTHESIS OF INDOLE ALKALOIDS. A TOTAL SYNTHESIS OF (±)-ASPIDOFRACTININE

  摘要：

  事实证明，新的酰化剂[PhS(O)-CH=C(OMe)Cl 和相应的砜]可以通过双碳迈克尔受体将乙酰基诱导到羰基的 α 位，并成功地应用于 (±)-aspidofractinine 的全合成。

  DOI：

  10.1246/cl.1986.927

文献信息

• Collective Total Synthesis of Aspidofractinine Alkaloids through the Development of a Bischler–Napieralski/Semipinacol Rearrangement Reaction
  作者：Shuang‐Hu Wang、Rui‐Qi Si、Qing‐Bo Zhuang、Xiang Guo、Tian Ke、Xiao‐Ming Zhang、Fu‐Min Zhang、Yong‐Qiang Tu

  DOI：10.1002/anie.202009238

  日期：2020.12

  A tandem Bischler–Napieralski/semipinacol rearrangement reaction has been developed for the purpose of assembling a bis(spirocyclic) indole framework, a privileged structural unit of aspidofractinine‐type monoterpenoid indole alkaloids, and was used in combination with a subsequent Mannich reaction to expeditiously construct the central bridged bicyclo[2.2.1]heptane ring system of these molecules with

  已经开发了串联的Bischler–Napieralski / semipinacol重排反应，目的是组装双（螺环）吲哚骨架（天冬氨酸吗啡型单萜吲哚生物碱的优先结构单元），并与随后的Mannich反应结合使用，以快速构建这些具有连续四元中心的分子的中心桥联双环[2.2.1]庚烷环系统。这种新策略的发展最终导致了四种aspaspfractinine生物碱的总全合成。
• APPLICATION OF THE NEW ACYLATING AGENTS [PhS(O)–CH=C(OMe)Cl AND PhSO₂–CH=C(OMe)Cl] TO THE SYNTHESIS OF INDOLE ALKALOIDS. A TOTAL SYNTHESIS OF (±)-ASPIDOFRACTININE
  作者：Hitoshi Kinoshita、Takeshi Ohnuma、Takeshi Oishi、Yoshio Ban

  DOI：10.1246/cl.1986.927

  日期：1986.6.5

  The new acylating agents [PhS(O)–CH=C(OMe)Cl and the corresponding sulfone] were proved to be useful for indroduction of an acetyl group into the α-position of the carbonyl group by means of two-carbon Michael acceptors, which was successfully applied to a total synthesis of (±)-aspidofractinine.

  事实证明，新的酰化剂[PhS(O)-CH=C(OMe)Cl 和相应的砜]可以通过双碳迈克尔受体将乙酰基诱导到羰基的 α 位，并成功地应用于 (±)-aspidofractinine 的全合成。
• Total Synthesis of (.+-.)-Aspidofractinine and (.+-.)-Aspidospermidine
  作者：Ernest Wenkert、Song Liu

  DOI：10.1021/jo00104a023

  日期：1994.12

  Functional group manipulations on a previously constructed, easily accessible deethylaspidospermidine derivative have transformed the latter in few steps into a ring E diene, whose Diels-Alder reaction with phenyl vinyl sulfone and subsequent reductions has led to (+/-)-aspidofractinine. One-bond unraveling of a (phenylsulfonyl)aspidofractinine intermediate, followed by reductions, provided a second-generation pathway to (+/-)-aspidospermidine.
• Cyclization of Oxindolic methylketones with acid : A rapid synthesis of (±)-aspidofractinine
  作者：Dominique Cartier、Mohammed Ouahrani、Jean Lévy

  DOI：10.1016/s0040-4039(00)99622-9

  日期：1989.1
• Total Syntheses of (−)‐Minovincine and (−)‐Aspidofractinine through a Sequence of Cascade Reactions
  作者：Szilárd Varga、Péter Angyal、Gábor Martin、Orsolya Egyed、Tamás Holczbauer、Tibor Soós

  DOI：10.1002/anie.202004769

  日期：2020.8.3

  8‐step syntheses of (−)‐minovincine and (−)‐aspidofractinine using easily available and inexpensive reagents and catalyst. A key element of the strategy was the utilization of a sequence of cascade reactions to rapidly construct the penta‐ and hexacyclic frameworks. These cascade transformations included organocatalytic Michael‐aldol condensation, a multistep anionic Michael‐SN2 cascade reaction, and

  我们报告了使用容易获得和廉价的试剂和催化剂进行的（-）-氨基长春新碱和（-）-aspidofractinine的8步合成。该策略的关键要素是利用一系列级联反应快速构建五环和六环框架。这些级联的变换包括有机催化迈克尔-醇醛缩合，一个多阴离子迈克尔-S Ñ 2级联反应，和曼尼希反应中断Fischer吲哚。为了简化合成路线，我们还研究了空间效应的故意使用，以确保各种化学和区域选择性转化。