(1S,3aS,4R,4aS,9aS)-1-Acetoxymethyl-3-oxo-1,3,3a,4,4a,5,6,7,8,9a-decahydro-benzo[f]isoindole-2,4-dicarboxylic acid 2-benzyl ester | 183663-31-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: (1S,3aS,4R,4aS,9aS)-1-Acetoxymethyl-3-oxo-1,3,3a,4,4a,5,6,7,8,9a-decahydro-benzo[f]isoindole-2,4-dicarboxylic acid 2-benzyl ester
• 英文别名: (3S,3aS,8aS,9R,9aS)-3-(acetyloxymethyl)-1-oxo-2-phenylmethoxycarbonyl-3a,5,6,7,8,8a,9,9a-octahydro-3H-benzo[f]isoindole-9-carboxylic acid
• CAS: 183663-31-2
• 化学式: C₂₄H₂₇NO₇
• 分子量: 441.481
• InChiKey: ZTEJHCXDZCUNHN-SSSFQFABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  110
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1S,3aS,4R,4aS,9aS)-1-Acetoxymethyl-3-oxo-1,3,3a,4,4a,5,6,7,8,9a-decahydro-benzo[f]isoindole-2,4-dicarboxylic acid 2-benzyl ester 在 三氟乙酸 作用下， 以 甲醇 、 水 为溶剂， 反应 10.0h， 以96%的产率得到(1S,3aS,4R,4aS,9aS)-1-Hydroxymethyl-3-oxo-1,3,3a,4,4a,5,6,7,8,9a-decahydro-benzo[f]isoindole-2,4-dicarboxylic acid 2-benzyl ester
  参考文献：
  名称：

  Diels−Alder Reactions of Chiral 1,3-Dienes

  摘要：

  Structurally related 1,3-dienes 3a-f attached to a chiral carbon were treated with maleic anhydride under a variety of conditions. The initial Diels-Alder adducts were not isolated as they spontaneously rearranged to the isomeric isoindolones 6 and 7. The rate of the rearrangement was dependent on the relative stereochemistry of the initial cycloadducts. The pi-facial selectivity of the Diels-Alder reaction was determined by analyzing reaction mixtures of the isomeric isoindolones by H-1 and C-13 NMR spectroscopy and HPLC. A gradual increase in the ct-facial selectivity was observed when the homoallylic hydroxyl group of the diene was endowed with a larger protecting group or slightly increased by performing the reactions in ether saturated with LiClO4. These effects were rationalized by proposing a model based on 1,3-allylic strain in the transition state for the dienes 3a-f.

  DOI：

  10.1021/jo9609743
• 作为产物：
  描述：

  马来酸酐 、 L-2-<(benzyloxycarbonyl)amino>-4-(cyclohex-1-en-1-yl)but-3-enyl acetate 以 various solvent(s) 为溶剂， 反应 1.0h， 生成 (1S,3aR,4S,4aR,9aR)-1-Acetoxymethyl-3-oxo-1,3,3a,4,4a,5,6,7,8,9a-decahydro-benzo[f]isoindole-2,4-dicarboxylic acid 2-benzyl ester 、 (1S,3aS,4R,4aS,9aS)-1-Acetoxymethyl-3-oxo-1,3,3a,4,4a,5,6,7,8,9a-decahydro-benzo[f]isoindole-2,4-dicarboxylic acid 2-benzyl ester
  参考文献：
  名称：

  Diels−Alder Reactions of Chiral 1,3-Dienes

  摘要：

  Structurally related 1,3-dienes 3a-f attached to a chiral carbon were treated with maleic anhydride under a variety of conditions. The initial Diels-Alder adducts were not isolated as they spontaneously rearranged to the isomeric isoindolones 6 and 7. The rate of the rearrangement was dependent on the relative stereochemistry of the initial cycloadducts. The pi-facial selectivity of the Diels-Alder reaction was determined by analyzing reaction mixtures of the isomeric isoindolones by H-1 and C-13 NMR spectroscopy and HPLC. A gradual increase in the ct-facial selectivity was observed when the homoallylic hydroxyl group of the diene was endowed with a larger protecting group or slightly increased by performing the reactions in ether saturated with LiClO4. These effects were rationalized by proposing a model based on 1,3-allylic strain in the transition state for the dienes 3a-f.

  DOI：

  10.1021/jo9609743