(M,1S)-1-methyl-19-[4-(4-propylcyclohexyl)phenyl]-1,3,16,17-tetrahydrobenzo[5,6]phenanthro[3,4-c]naphtho[1,2-e]oxepine

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (M,1S)-1-methyl-19-[4-(4-propylcyclohexyl)phenyl]-1,3,16,17-tetrahydrobenzo[5,6]phenanthro[3,4-c]naphtho[1,2-e]oxepine
• 英文别名: (19S)-19-methyl-17-[4-(4-propylcyclohexyl)phenyl]-20-oxaheptacyclo[16.13.0.02,15.03,12.04,9.022,31.025,30]hentriaconta-1,3(12),4,6,8,10,15,17,22(31),23,25,27,29-tridecaene
• 化学式: C₄₆H₄₄O
• 分子量: 612.855
• InChiKey: OAKXHDCLHBAICV-LRBNCQHVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.1
• 重原子数：
  47
• 可旋转键数：
  4
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-bromo-4-(4-propylcyclohexyl)benzene 在 双(乙腈)氯化钯(II) 、 四(三苯基膦)钯 、 carbon monoxide,cobalt,cyclopenta-1,3-diene copper(l) iodide 、 正丁基锂 、 四丁基氟化铵 、 碘 、 potassium hydride 、 二异丙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 癸烷 、 甲苯 为溶剂， 反应 13.0h， 生成 (M,1S)-1-methyl-19-[4-(4-propylcyclohexyl)phenyl]-1,3,16,17-tetrahydrobenzo[5,6]phenanthro[3,4-c]naphtho[1,2-e]oxepine
  参考文献：
  名称：

  Asymmetric Synthesis of [7]Helicene-Like Molecules

  摘要：

  A new approach to nonracemic [7]helicene-like molecules has been developed. Stereoselective Col-mediated [2 + 2 + 2] cycloisomerization of aromatic triynes containing an asymmetric carbon atom produces [7]helicene-like scaffolds in diastereomeric ratios up to 100:0. This central-to-helical chirality transfer can be controlled by the absolute configuration at the asymmetric center and by the presence of carbon substituents.

  DOI：

  10.1021/ol047311p

文献信息

• On the Origin of Diastereoselectivity in [2 + 2 + 2] Cycloisomerization of Chiral Triynes:  Controlling Helicity of Helicene-like Compounds by Thermodynamic Factors
  作者：Petr Sehnal、Zuzana Krausová、Filip Teplý、Irena G. Stará、Ivo Starý、Lubomír Rulíšek、David Šaman、Ivana Císařová

  DOI：10.1021/jo701997p

  日期：2008.3.1

  selected helicene-like compounds were measured indicating their lower configurational stability in comparison to the parent carbohelicenes. Free energy differences between corresponding pairs of diastereomers (calculated at the DFT B3LYP/TZV+P level) were in excellent agreement with the experimental data and allowed for the prediction of the stereochemical outcome of the reaction. An optically pure hexacyclic

  研究了CH 3 O取代的旋光纯芳族三炔的非对映选择性Co I介导的[2 + 2 + 2]环异构化，以得到非外消旋官能化的类似螺旋的化合物（包括五，六和七环螺旋支架）。使用CpCo（CO）2在140°C下反应的立体化学结果受热力学因素控制，产生的非对映异构体比例高达91：9。使用CpCo（乙烯）2在室温下，进行动力学控制导致立体选择性的损失。测量了对于所选的类螺旋烯化合物的差向异构化的障碍，表明与母体碳螺旋烯相比，它们的构型稳定性较低。相应的非对映异构体对之间的自由能差异（以DFT B3LYP / TZV + P水平计算）与实验数据高度吻合，可以预测反应的立体化学结果。以数克规模制备了光学纯的六环类螺旋烯状醇。它的X射线结构证实了以前的螺旋度分配基于ROESY 1 H NMR光谱中的1 H- 1 H相关性。
• Asymmetric Synthesis of [7]Helicene-Like Molecules
  作者：Irena G. Stará、Zuzana Alexandrová、Filip Teplý、Petr Sehnal、Ivo Starý、David Šaman、Miloš Buděšínský、Josef Cvačka

  DOI：10.1021/ol047311p

  日期：2005.6.1

  A new approach to nonracemic [7]helicene-like molecules has been developed. Stereoselective Col-mediated [2 + 2 + 2] cycloisomerization of aromatic triynes containing an asymmetric carbon atom produces [7]helicene-like scaffolds in diastereomeric ratios up to 100:0. This central-to-helical chirality transfer can be controlled by the absolute configuration at the asymmetric center and by the presence of carbon substituents.