echinopine A | 1013026-40-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: echinopine A
• 英文别名: (+)-Echinopine A；2-[(1R,2R,4R,7R,12R)-8-methylidene-2-tetracyclo[5.3.2.02,4.04,12]dodecanyl]acetic acid
• CAS: 1013026-40-8
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: XODFJJSIJDSDCR-OGMFBOKVSA-N

物化性质

• 熔点：
  104-105 °C(Solvent: Ethyl acetate)
• 沸点：
  379.3±11.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲醇 、 echinopine A 在 三甲基硅烷化重氮甲烷 作用下， 以 乙醚 、 苯 为溶剂， 反应 0.5h， 以94%的产率得到echinopine B
  参考文献：
  名称：

  Total Syntheses of Echinopines

  摘要：

  A concise and scalable synthesis of a cis-fused bicyclo[5.3.0]decane ring system has been developed for the total synthesis of echinopines. The core of the natural products was constructed efficiently through an intramolecular 1,3-dipolar cycloaddition and ring contraction strategy.

  DOI：

  10.1021/ol400645v
• 作为产物：
  描述：

  (1R,2R,4R,7R,12R)-8-methylidenetetracyclo[5.3.2.02,4.04,12]dodecane-2-carboxylic acid 在 silver benzoate 、 三乙胺 、 三氯乙腈 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 9.0h， 生成 echinopine A
  参考文献：
  名称：

  Total Syntheses of Echinopines

  摘要：

  A concise and scalable synthesis of a cis-fused bicyclo[5.3.0]decane ring system has been developed for the total synthesis of echinopines. The core of the natural products was constructed efficiently through an intramolecular 1,3-dipolar cycloaddition and ring contraction strategy.

  DOI：

  10.1021/ol400645v

文献信息

• Total Synthesis of Echinopines A and B
  作者：K. C. Nicolaou、Hanfeng Ding、Jean-Alexandre Richard、David Y.-K. Chen

  DOI：10.1021/ja9093988

  日期：2010.3.24

  Echinopines A and B [(+)-1 and (+)-2], two naturally occurring compounds characterized with a unique [3.5.5.7] carbon framework, have been synthesized in both enantiomeric and racemic forms. Their total synthesis involves a novel intramolecular rhodium-catalyzed cyclopropanation (4 --> 16) and a samarium diiodide-mediated ring closure (3 --> 37).

  Echinopines A 和 B [(+)-1 和 (+)-2] 是两种天然存在的化合物，具有独特的 [3.5.5.7] 碳骨架，已以对映体和外消旋形式合成。他们的全合成涉及新型分子内铑催化的环丙烷化反应 (4 --> 16) 和二碘化钐介导的闭环 (3 --> 37)。
• Total Syntheses of (+)-Echinopine A and B: Determination of Absolute Stereochemistry
  作者：Thomas Magauer、Johann Mulzer、Konrad Tiefenbacher

  DOI：10.1021/ol902263k

  日期：2009.11.19

  The first total syntheses of the novel 3,5,5,7-sesquiterpenoids (+)-Echinopine A (1) and B (2) were achieved. Thereby the proposed structures were confirmed, and the absolute stereochemistry was determined. The key features are (1) the stereoselective installation of the vinyl-moiety on the concave side of the bicyclo[3.3.0]octane core via Myers’ [3,3]-sigmatropic rearrangement, (2) the finding that

  首次新颖的3,5,5,7-倍半萜（+）-Echinopine A（1）和B（2）的总合成。从而证实了所提出的结构，并确定了绝对立体化学。主要特征是（1）通过Myers的[3,3]-σ重排将乙烯基部分立体选择性地安装在双环[3.3.0]辛烷核的凹入侧，（2）发现取代基在在基本条件下，可以将酮旁边的C7位置差向至所需的凹面，（3）通过RCM关闭高度应变的七元环，以及（4）乙烯基三氟甲磺酸酯与乙烯酮的不寻常的C2同源性甲硅烷基乙缩醛。
• A Synthesis of Echinopine B
  作者：Theo D. Michels、Matthew S. Dowling、Christopher D. Vanderwal

  DOI：10.1002/anie.201203147

  日期：2012.7.23

  In a short synthesis of echinopine B, a guaiane‐like intermediate was generated through a methylenecyclopentane annulation onto a substituted cycloheptenone. The resulting bicyclic compound was converted into the natural product by a PtCl2‐catalyzed enyne cycloisomerization (see scheme). Several late‐stage polycyclic rearrangement products were isolated and characterized.

  在棘手类松果碱B的短合成中，通过亚甲基环戊烷环合到取代的环庚烯酮上生成了愈创树状中间体。所得的双环化合物通过PtCl 2催化的烯炔环异构化转化为天然产物（参见方案）。分离并鉴定了几种晚期多环重排产物。
• Total Syntheses of Echinopines
  作者：Wenbo Xu、Shuming Wu、Lili Zhou、Guangxin Liang

  DOI：10.1021/ol400645v

  日期：2013.4.19

  A concise and scalable synthesis of a cis-fused bicyclo[5.3.0]decane ring system has been developed for the total synthesis of echinopines. The core of the natural products was constructed efficiently through an intramolecular 1,3-dipolar cycloaddition and ring contraction strategy.