9,11,12,13,13a,14-hexahydro-3,6,7-trimethoxy-13a-methyldibenzo[f,h]pyrrolo[1,2-b]-isoquinoline

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 9,11,12,13,13a,14-hexahydro-3,6,7-trimethoxy-13a-methyldibenzo[f,h]pyrrolo[1,2-b]-isoquinoline
• 英文别名: (±)-3,6,7-trimethoxy-13a-methyl-9,11,12,13,13a,14-hexahydrodibenzo[f,h]pyrrolo[1,2-b]isoquinoline；3,6,7-trimethoxy-13a-methyl-11,12,13,14-tetrahydro-9H-phenanthro[9,10-f]indolizine
• 化学式: C₂₄H₂₇NO₃
• 分子量: 377.483
• InChiKey: LUMXWWHPHXBKPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  30.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  4-甲基-4-戊酸 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 草酰氯 、 过氧化双月桂酰 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 9.0h， 生成 9,11,12,13,13a,14-hexahydro-3,6,7-trimethoxy-13a-methyldibenzo[f,h]pyrrolo[1,2-b]-isoquinoline
  参考文献：
  名称：

  Total Synthesis of Phenanthroindolizidine Alkaloids through an Amidyl Radical Cascade/Rearrangement Reaction

  摘要：

  A short and general synthesis of the phenanthroindolizidine alkaloids is reported, featuring an unusual amidyl radical 5-exo/5-exo/rearrangement cascade of a xanthate precursor. Second, using an amidyl radical 5-exo/6-endo cascade to synthesize a phenanthroindolizidine alkaloid exclusively has been developed through a small structural modification.

  DOI：

  10.1021/ol4025925

文献信息

• Oxazaborolidine-catalyzed reductive parallel kinetic resolution of ketones from β-nitro-azabicycles for the synthesis of chiral hypoestestatins 1, 2
  作者：Wannaporn Disadee、Somsak Ruchirawat

  DOI：10.1039/d1ob01608c

  日期：——

  Finally, the desired product was obtained via a formal reductive removal of the hydroxyl group. This methodology has been applied for the synthesis of 13a-methyl tylophora alkaloids in up to 65% yield over six steps from β-nitro-azabicycles. Both natural and unnatural enantioenriched hypoestestatins 1 and 2, and related compounds were synthesized using parallel kinetic resolution of the CBS-oxazaborolidine-catalyzed

  报道了一种合成 13a-甲基 tylophora 生物碱的新方法。主要特征包括两种不同的合成途径，旨在将 β-硝基氮杂双环转化为菲核心。成功的步骤包括将硝基哌啶部分氧化为相应的α,β-不饱和酮，以及形成菲环的氧化联芳基偶联反应。最后，通过正式还原除去羟基得到所需产物。该方法已应用于从 β-硝基氮杂二环化合物合成 13a-甲基 tylophora 生物碱，六步收率高达 65%。天然和非天然对映体富集的下雌睾酮 1 和 2 以及相关化合物均通过 CBS-恶唑硼烷催化外消旋酮还原的平行动力学拆分合成，以提供两种可分离的非对映醇，总产率高达 91%，并且具有高对映选择性（高达89% ee）。此外，首次报道了催化不对称还原为seco -hypoestestatins 1和2。因此，将外消旋混合物开发为两种对映体富集形式的能力为未来的各种生物测定提供了益处。
• Synthesis of 13a-methylphenanthroindolizidines using radical cascade cyclization: synthetic studies toward (±)-hypoestestatin 1
  作者：Kosuke Takeuchi、Atsuko Ishita、Jun-ichi Matsuo、Hiroyuki Ishibashi

  DOI：10.1016/j.tet.2007.08.030

  日期：2007.11

  A radical cascade involving 6-endo cyclization of aryl radicals generated from N-acryloyl-N-(1-methylethenyl)-9-bromophenanthren-10-ylmethylamines, followed by 5-endo-trig cyclization of the resulting alpha-amidoyl radicals afforded phenanthroindolizidines bearing a methyl substituent at the angular C13a position. 2,3,6-Trimethoxy derivative was synthesized by using this method, but its spectral data were not in accord with those of literature values reported for hypoestestatin 1. Further synthetic study toward hypoestestatin 1 is demonstrated. (c) 2007 Elsevier Ltd. All rights reserved.
• Total Synthesis of Phenanthroindolizidine Alkaloids through an Amidyl Radical Cascade/Rearrangement Reaction
  作者：Guifang Han、Yuxiu Liu、Qingmin Wang

  DOI：10.1021/ol4025925

  日期：2013.10.18

  A short and general synthesis of the phenanthroindolizidine alkaloids is reported, featuring an unusual amidyl radical 5-exo/5-exo/rearrangement cascade of a xanthate precursor. Second, using an amidyl radical 5-exo/6-endo cascade to synthesize a phenanthroindolizidine alkaloid exclusively has been developed through a small structural modification.