(1S,1'S,6R,6'R,7R,7'R,8R,8'R)-N,N'-bis(7-ethynylbicyclo<4.3.0>nonan-8-yl)-1,3-diaminopropane | 159303-41-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (1S,1'S,6R,6'R,7R,7'R,8R,8'R)-N,N'-bis(7-ethynylbicyclo<4.3.0>nonan-8-yl)-1,3-diaminopropane
• 英文别名: N,N'-bis[(1R,2R,3aS,7aR)-1-ethynyl-2,3,3a,4,5,6,7,7a-octahydro-1H-inden-2-yl]propane-1,3-diamine
• CAS: 159303-41-0
• 化学式: C₂₅H₃₈N₂
• 分子量: 366.59
• InChiKey: CPLKIOHPKOKYIU-LMPFRRRQSA-N

物化性质

• 沸点：
  489.9±45.0 °C(predicted)
• 密度：
  1.03±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.21
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  24.06
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1S,1'S,6R,6'R,7R,7'R,8R,8'R)-N,N'-bis(7-ethynylbicyclo<4.3.0>nonan-8-yl)-1,3-diaminopropane 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 air 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 生成 巴布胺
  参考文献：
  名称：

  （-）-巴布胺和（-）-卤代丙二胺的总合成。

  摘要：

  五环海洋生物碱（-）-巴胺（1）和（-）-卤代二胺（2）是通过全合成制备的。合成开始于（-）-8，其通过双甲磺酸酯17，二腈18和二酸19转化为二酯20。狄克曼环化20提供了酮酸酯21，将其转化为缩醛22。缩醛酮25用1，3-丙二胺和三乙酰氧基硼氢化钠进行还原胺化，得到二胺26和27，为非对映异构体的71∶29混合物，有利于具有木瓜胺相对构型的对称异构体。将二胺转化为它们的t-Boc衍生物后，将苄基醚裂解，并将生成的二醇氧化为二醛30。应用Seyferth方法将醛转化为炔烃，得到二炔31和32的混合物。从31除去t-Boc保护基后，将二氨基二炔15用三丁基锡烷和偶氮异丁腈处理，得到双乙烯基锡烷34。在空气存在下，将这种化合物与Pd（II）和Cu（I）合成，生成（-）-巴布胺（1）。从不对称异构体32获得（-）-卤代二胺（2）。合成生物碱的NMR谱图与天然生物碱的真实样品的NMR谱图相同。

  DOI：

  10.1021/jo951647i
• 作为产物：
  描述：

  {(1S,2R)-2-[3-(Dimethyl-phenyl-silanyl)-propa-1,2-dienyl]-cyclohexyl}-acetonitrile 在 四丁基氟化铵 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 16.0h， 生成 (1S,1'S,6R,6'R,7R,7'R,8R,8'R)-N,N'-bis(7-ethynylbicyclo<4.3.0>nonan-8-yl)-1,3-diaminopropane
  参考文献：
  名称：

  Total Synthesis of Papuamine via a Stereospecific Intramolecular Imino Ene Reaction of an Allenylsilane

  摘要：

  DOI：

  10.1021/ja00100a070

文献信息

• Total Synthesis of the Unusual Marine Alkaloid (-)-Papuamine Utilizing a Novel Imino Ene Reaction
  作者：Robert M. Borzilleri、Steven M. Weinreb、Masood Parvez

  DOI：10.1021/ja00149a013

  日期：1995.11

  A concise enantioselective total synthesis of the recently isolated antibacterial and antifungal marine alkaloid (-)-papuamine (1) is described. The key feature of the synthesis includes the development and subsequent implementation of a novel pericyclic imino ene reaction. Starting from readily available enantiomerically pure acid ester 11, allenyl silane N-benzyl imines 24 and 27 were generated in situ from aldehydes 23a/b. These imines undergo concerted stereospecific imino ene reactions to afford silyl acetylenes 25 and 28, respectively, in high yields. The ene reactions were found to be promoted both thermally in refluxing toluene and at lower temperatures using the Lewis acid stannic chloride as a catalyst. Desilylation of compounds 25 and 28 afforded terminal alkynes 26 and 29, respectively, whose structures and stereochemistry were unambiguously established by single crystal X-ray structure analysis of the corresponding HCl salts. In a more highly convergent approach to the alkaloid 1, aldehyde allenyl silane 23a was treated with 0.5 equiv of 1,3-diaminopropane in refluxing toluene to afford homopropargylic diamine 40 as one stereoisomer via a double imino ene reaction, which effectively established the remaining four of the eight stereogenic centers of papuamine in one simple operation. To complete the route to the natural enantiomer of papuamine, a Pd(II) catalyzed macrocyclization of bis-E-vinyl stannane 42b was effected in moderate yield.