indolo[1,2-a]octahydro-1-thia-3a-azacyclopenta[d]naphthylen-3-one | 144633-21-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: indolo[1,2-a]octahydro-1-thia-3a-azacyclopenta[d]naphthylen-3-one
• 英文别名: 20-Thia-10,17-diazapentacyclo[11.7.0.01,17.02,10.04,9]icosa-2,4,6,8-tetraen-18-one
• CAS: 144633-21-6
• 化学式: C₁₇H₁₈N₂OS
• 分子量: 298.409
• InChiKey: ZWNSCHSPROLHKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  50.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  indolo[1,2-a]octahydro-1-thia-3a-azacyclopenta[d]naphthylen-3-one 在 sodium periodate 、 乙酸酐 、 对甲苯磺酸 作用下， 以 1,4-二氧六环 、 甲醇 、 水 、 甲苯 为溶剂， 反应 25.0h， 生成 10,17-diaza-20-thiahexacyclo[11.7.0^1,17.0^2,10.0^3,19.0^4,9]icosa-2(3),4(9),5,7-tetraen-18-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
• 作为产物：
  描述：

  3-((2-indol-1-yl)ethyl)piperidin-2-one 在 劳森试剂 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 4.0h， 生成 indolo[1,2-a]octahydro-1-thia-3a-azacyclopenta[d]naphthylen-3-one
  参考文献：
  名称：

  Cycloaddition Chemistry of Anhydro-4-hydroxy-1,3-thiazolium Hydroxides (Thioisomünchnones) for the Synthesis of Heterocycles

  摘要：

  一系列的α,α-二取代硫代异肟酮通过在三乙胺存在下，用溴乙酰氯处理非环状或环状硫代酰胺来制备。结果发现，这些介离子偶极体会发生双分子1,3-偶极环加成反应与多种不同的偶极体分子。当硫代酰胺的α-位上有氢原子时，最初形成的N-酰基亚胺离子会快速失去质子，产生S,N-酮烯醇缩醛，比形成硫代异肟酮的速度更快。还研究了几种带有附加烯烃的取代硫代异肟酮的环加成行为。内向环加成反应是邻近的π键跨过瞬态硫代异肟酮偶极子的结果，这是分子内反应的立体化学产物的成因。分子力学计算表明，内向非对映异构体的能量比相应的向外构体显著更低。尝试将硫代异肟酮偶极子环加成到附加的吲哚环上未能成功。相反，高产率地形成通过吲哚环以亲核方式环化到硫代N-酰基亚胺离子上的产物。

  DOI：

  10.1055/s-1994-25621

文献信息

• π-Cyclization reactions of thio N-acyliminium ions for heterocyclic synthesis
  作者：Scott M. Sheehan、L. Scott Beall、Albert Padwa

  DOI：10.1016/s0040-4039(98)00902-2

  日期：1998.7

  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.