[(E)-(S)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-3-cyclohex-1-enyl-allyl]-carbamic acid benzyl ester | 182890-45-5

• 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: [(E)-(S)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-3-cyclohex-1-enyl-allyl]-carbamic acid benzyl ester
• 英文别名: benzyl N-[(E,2S)-1-[tert-butyl(diphenyl)silyl]oxy-4-(cyclohexen-1-yl)but-3-en-2-yl]carbamate
• CAS: 182890-45-5
• 化学式: C₃₄H₄₁NO₃Si
• 分子量: 539.79
• InChiKey: QWMVMZVZGANCOK-JCTIBXOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.91
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  马来酸酐 、 [(E)-(S)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-3-cyclohex-1-enyl-allyl]-carbamic acid benzyl ester 在 4A MS 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以63%的产率得到(1S,3aS,4R,4aS,9aS)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-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：

  (2S)-2-but-3-en-1-ol 在 palladium diacetate 、 四丁基三氟甲磺酸铵 、 potassium carbonate 、 1-羟基苯并三唑 、 pyridine triethylamine 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 54.0h， 生成 [(E)-(S)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-3-cyclohex-1-enyl-allyl]-carbamic acid benzyl ester
  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

• 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.