10b-(3,4-dimethoxybenzyl)-8,9-dimethoxy-6,10b-dihydro-5H-thiazolo[2,3-a]isoquinolin-3-one | 269407-38-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: 10b-(3,4-dimethoxybenzyl)-8,9-dimethoxy-6,10b-dihydro-5H-thiazolo[2,3-a]isoquinolin-3-one
• 英文别名: 10b-[(3,4-Dimethoxyphenyl)methyl]-8,9-dimethoxy-5,6-dihydro-[1,3]thiazolo[2,3-a]isoquinolin-3-one
• CAS: 269407-38-7
• 化学式: C₂₂H₂₅NO₅S
• 分子量: 415.51
• InChiKey: FWZGNNORNSHLNC-UHFFFAOYSA-N

物化性质

• 沸点：
  594.4±50.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  82.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  10b-(3,4-dimethoxybenzyl)-8,9-dimethoxy-6,10b-dihydro-5H-thiazolo[2,3-a]isoquinolin-3-one 在 镍 作用下， 以 乙醇 为溶剂， 反应 15.0h， 以68%的产率得到1-[1-[(3,4-二甲氧基苯基)甲基]-6,7-二甲氧基-3,4-二氢-1H-异喹啉-2-基]乙酮
  参考文献：
  名称：

  A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems

  摘要：

  A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.

  DOI：

  10.1021/jo991742h
• 作为产物：
  描述：

  (3,4-二甲氧基苯基)乙酰氯 在 劳森试剂 、 三氟乙酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 73.0h， 生成 10b-(3,4-dimethoxybenzyl)-8,9-dimethoxy-6,10b-dihydro-5H-thiazolo[2,3-a]isoquinolin-3-one
  参考文献：
  名称：

  A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems

  摘要：

  A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.

  DOI：

  10.1021/jo991742h