(4aS,8R,8aR)-8-Vinyl-3,4,4a,7,8,8a-hexahydro-isochromen-1-one | 130760-67-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (4aS,8R,8aR)-8-Vinyl-3,4,4a,7,8,8a-hexahydro-isochromen-1-one
• CAS: 130760-67-7
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: ANTQBTLZNOJQKZ-IVZWLZJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.93
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (4aS,8R,8aR)-8-Vinyl-3,4,4a,7,8,8a-hexahydro-isochromen-1-one 在 一水合肼 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以87%的产率得到(1R,2S,6R)-2-(2-Hydroxy-ethyl)-6-vinyl-cyclohex-3-enecarboxylic acid hydrazide
  参考文献：
  名称：

  A Diels-Alder approach to Stemona alkaloids: total synthesis of stenine

  摘要：

  A total synthesis of dl-stenine (4) is described. Key features involve (1) use of an intramolecular Diels-Alder cycloaddition-aminimide rearrangement sequence to construct the perhydroindole substructure (29 --> 36 --> 27), (2) application of an Eschenmoser-Claisen rearrangement-iodolactonization sequence to prepare the butenolide substructure (58 --> 59 --> 61), (3) use of a free-radical allylation to introduce the C(9)-ethyl group (61 --> 62), and (4) thermal cyclization of an amino ester to afford azepinone 68. A variety of intermolecular and intramolecular Diels-Alder reactions, including examples in which alpha,beta-unsaturated thioesters play the role of dienophile, are also described.

  DOI：

  10.1021/jo00067a015
• 作为产物：
  描述：

  trans 2,4-pentadienoyl chloride 在 正丁基锂 、 氯化二乙基铝 作用下， 以 氯仿 为溶剂， 反应 21.5h， 生成 (4aS,8R,8aR)-8-Vinyl-3,4,4a,7,8,8a-hexahydro-isochromen-1-one
  参考文献：
  名称：

  A Diels-Alder approach to Stemona alkaloids: total synthesis of stenine

  摘要：

  A total synthesis of dl-stenine (4) is described. Key features involve (1) use of an intramolecular Diels-Alder cycloaddition-aminimide rearrangement sequence to construct the perhydroindole substructure (29 --> 36 --> 27), (2) application of an Eschenmoser-Claisen rearrangement-iodolactonization sequence to prepare the butenolide substructure (58 --> 59 --> 61), (3) use of a free-radical allylation to introduce the C(9)-ethyl group (61 --> 62), and (4) thermal cyclization of an amino ester to afford azepinone 68. A variety of intermolecular and intramolecular Diels-Alder reactions, including examples in which alpha,beta-unsaturated thioesters play the role of dienophile, are also described.

  DOI：

  10.1021/jo00067a015

文献信息

• Total synthesis of (dl)-stenine
  作者：Cheng Yi Chen、David J. Hart

  DOI：10.1021/jo00313a003

  日期：1990.12

  Intramolecular Diels-Alder cycloadduct 10 was converted to the Stemona alkaloid stenine (1) via a reaction sequence that features a Curtius rearrangement (12 --> 13), Eschenmoser-Claisen rearrangement (19 --> 20) and stereoselective free radical allylation (4 --> 21).