6,7-dimethoxy-2,2a,3,4-tetrahydro-1H-9-thia-11a-azapentaleno[6a,1a]naphthalen-11-one | 211557-65-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并吡喃类
• 英文名称: 6,7-dimethoxy-2,2a,3,4-tetrahydro-1H-9-thia-11a-azapentaleno[6a,1a]naphthalen-11-one
• 英文别名: 4,5-Dimethoxy-16-thia-13-azatetracyclo[8.6.0.01,13.02,7]hexadeca-2,4,6-trien-14-one
• CAS: 211557-65-2
• 化学式: C₁₆H₁₉NO₃S
• 分子量: 305.398
• InChiKey: YFAKTZGOCFMXMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  64.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6,7-dimethoxy-2,2a,3,4-tetrahydro-1H-9-thia-11a-azapentaleno[6a,1a]naphthalen-11-one 在 镍 作用下， 以91%的产率得到7,8-dimethoxy-3,3a,4,5-tetrahydro-2H-benzo[g]indole
  参考文献：
  名称：

  π-Cyclization reactions of thio N-acyliminium ions for heterocyclic synthesis

  摘要：

  Thio N-acyliminium ions are readily generated from the reaction of thioamides with bromoacetyl chloride. In the presence of tethered pi-nucleophiles, cyclization occurs to give S,N-acetals which can be further converted into various alkaloid skeletons. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00902-2
• 作为产物：
  描述：

  3-[2-(3,4-dimethoxyphenyl)ethyl]pyrrolidin-2-one 在 劳森试剂 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 6.0h， 生成 6,7-dimethoxy-2,2a,3,4-tetrahydro-1H-9-thia-11a-azapentaleno[6a,1a]naphthalen-11-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