L-2-<(benzyloxycarbonyl)amino>-4-(cyclohex-1-en-1-yl)but-3-enyl acetate | 142952-93-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: L-2-<(benzyloxycarbonyl)amino>-4-(cyclohex-1-en-1-yl)but-3-enyl acetate
• 英文别名: (2S,3E)-2--4-(1'-cyclohexen-1'-yl)but-3-en-1-yl acetate；[(E,2S)-4-(cyclohexen-1-yl)-2-(phenylmethoxycarbonylamino)but-3-enyl] acetate
• CAS: 142952-93-0
• 化学式: C₂₀H₂₅NO₄
• 分子量: 343.423
• InChiKey: MNAIRZSBCUUOCU-HYSAVQALSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  25
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  L-2-<(benzyloxycarbonyl)amino>-4-(cyclohex-1-en-1-yl)but-3-enyl acetate 在 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 22.0h， 生成 (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：

  1-环状己烯三氟甲烷磺酸 、 (2S)-2-but-3-enyl acetate 在 palladium diacetate 、 四丁基三氟甲磺酸铵 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以80%的产率得到L-2-<(benzyloxycarbonyl)amino>-4-(cyclohex-1-en-1-yl)but-3-enyl acetate
  参考文献：
  名称：

  非活化烯烃的Heck偶联

  摘要：

  受保护的2-氨基丁-3-烯-1-醇与三氟甲磺酸环己烯基的Heck偶联可使用“无配体”的钯催化剂，碳酸钾和三氟甲磺酸四丁铵容易地进行。

  DOI：

  10.1016/0040-4020(96)00714-4

文献信息

• Palladium-catalyzed heck couplings of L-vinylglycine derivatives with vinyl and aryl halides and triflates.
  作者：Geoffrey T. Crisp、Peter T. Glink

  DOI：10.1016/s0040-4020(01)88492-1

  日期：1992.1

  The coupling of aryl and vinyl halides and triflates with L-vinylglycine derivatives under the influence of a palladium catalyst is described. The coupling is regioselective and stereoselective with the absolute configuration of the α-amino acid centre being retained.

  描述了在钯催化剂的影响下，芳基卤化物和乙烯基卤化物以及三氟甲磺酸酯与L-乙烯基甘氨酸衍生物的偶联。偶联是区域选择性和立体选择性的，保留了α-氨基酸中心的绝对构型。
• Heck couplings of non-activated alkenes
  作者：Geoffrey T. Crisp、Markus G. Gebauer

  DOI：10.1016/0040-4020(96)00714-4

  日期：1996.9

  The Heck couplings of protected 2-aminobut-3-en-1-ols with cyclohexenyl triflate can be readily carried out using a “ligand-free” palladium catalyst, potassium carbonate and tetrabutylammonium triflate.

  受保护的2-氨基丁-3-烯-1-醇与三氟甲磺酸环己烯基的Heck偶联可使用“无配体”的钯催化剂，碳酸钾和三氟甲磺酸四丁铵容易地进行。
• Diels−Alder Reactions of Chiral 1,3-Dienes
  作者：Geoffrey T. Crisp、Markus G. Gebauer

  DOI：10.1021/jo9609743

  日期：1996.1.1

  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.