(2R,3S,4R)-4-Benzyloxymethyl-2,3-dimethyl-2-((E)-3-oxo-but-1-enyl)-3-vinyl-cyclohexanone | 171625-12-0

• 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: (2R,3S,4R)-4-Benzyloxymethyl-2,3-dimethyl-2-((E)-3-oxo-but-1-enyl)-3-vinyl-cyclohexanone
• 英文别名: (2R,3S,4R)-3-ethenyl-2,3-dimethyl-2-[(E)-3-oxobut-1-enyl]-4-(phenylmethoxymethyl)cyclohexan-1-one
• CAS: 171625-12-0
• 化学式: C₂₂H₂₈O₃
• 分子量: 340.463
• InChiKey: GOHSJHRNJIPJOD-AZZRRPOBSA-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：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S,4R)-4-Benzyloxymethyl-2,3-dimethyl-2-((E)-3-oxo-but-1-enyl)-3-vinyl-cyclohexanone 在 potassium tert-butylate 、 nickel dichloride 、 锌 作用下， 以 四氢呋喃 、 乙二醇甲醚 、 水 为溶剂， 反应 39.0h， 生成 Nolen-Sprengeler lactone
  参考文献：
  名称：

  Tremorgenic Indole Alkaloids. 9. Asymmetric construction of an Advanced F-G-H-ring Lactone precursor for the Synthesis of Penitrem D

  摘要：

  Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (+/-)-12 was marked by low overall yield (<2%) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1% overall). The successful strategies exploited enolate generation via either conjugate additions to alpha,beta-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.

  DOI：

  10.1021/jo00129a025
• 作为产物：
  描述：

  (2R,3S,4R)-4-Benzyloxymethyl-2,3-dimethyl-2-[(E)-2-(2-methyl-[1,3]dioxolan-2-yl)-vinyl]-3-vinyl-cyclohexanone 在 4-甲基苯磺酸吡啶 作用下， 以 水 、 丙酮 为溶剂， 反应 24.0h， 以98%的产率得到(2R,3S,4R)-4-Benzyloxymethyl-2,3-dimethyl-2-((E)-3-oxo-but-1-enyl)-3-vinyl-cyclohexanone
  参考文献：
  名称：

  Tremorgenic Indole Alkaloids. 9. Asymmetric construction of an Advanced F-G-H-ring Lactone precursor for the Synthesis of Penitrem D

  摘要：

  Lactone (+)-12 is envisioned as the precursor to the F-G-H rings of penitrem D (4) in our ongoing synthetic venture. The efficient, stereocontrolled introduction of the vicinal quaternary methyl groups present the major challenge in the construction of this subunit. Our first route to (+/-)-12 was marked by low overall yield (<2%) and the instability of several key intermediates; these deficiencies were rectified in a second-generation approach that produced optically active material (18 steps from 19a, 2.1% overall). The successful strategies exploited enolate generation via either conjugate additions to alpha,beta-enones or the Evans oxy-Cope rearrangement as key regiochemical control elements.

  DOI：

  10.1021/jo00129a025