(2R,3S,4R)-4-Benzyloxymethyl-2,3-dimethyl-2-[(E)-2-(2-methyl-[1,3]dioxolan-2-yl)-vinyl]-3-vinyl-cyclohexanone | 171625-11-9

• 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)-2-(2-methyl-[1,3]dioxolan-2-yl)-vinyl]-3-vinyl-cyclohexanone
• 英文别名: (2R,3S,4R)-3-ethenyl-2,3-dimethyl-2-[(E)-2-(2-methyl-1,3-dioxolan-2-yl)ethenyl]-4-(phenylmethoxymethyl)cyclohexan-1-one
• CAS: 171625-11-9
• 化学式: C₂₄H₃₂O₄
• 分子量: 384.516
• InChiKey: FWSPCQQMOJFFLN-CYFRBXQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  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 potassium tert-butylate 、 4-甲基苯磺酸吡啶 、 nickel dichloride 、 锌 作用下， 以 四氢呋喃 、 乙二醇甲醚 、 水 、 丙酮 为溶剂， 反应 63.0h， 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：

  (3S,4R)-4-Benzyloxymethyl-3-methyl-2-[2-(2-methyl-[1,3]dioxolan-2-yl)-eth-(Z)-ylidene]-3-vinyl-cyclohexanone 、 碘甲烷 在 二苯基亚砜 、 potassium tert-butylate 作用下， 生成 (2R,3S,4R)-4-Benzyloxymethyl-2,3-dimethyl-2-[(E)-2-(2-methyl-[1,3]dioxolan-2-yl)-vinyl]-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

文献信息

• Tremorgenic Indole Alkaloids. 9. Asymmetric construction of an Advanced F-G-H-ring Lactone precursor for the Synthesis of Penitrem D
  作者：Amos B. Smith、Ernest G. Nolen、Ryuichi Shirai、Frances R. Blase、Mitsuaki Ohta、Noritaka Chida、Richard A. Hartz、Duke M. Fitch、William M. Clark、Paul A. Sprengeler

  DOI：10.1021/jo00129a025

  日期：1995.12

  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.