(E)-N-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-1-(8-methyl-1,4-dioxaspiro[4.5]decan-8-yl)methanimine | 244234-95-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-N-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-1-(8-methyl-1,4-dioxaspiro[4.5]decan-8-yl)methanimine
• CAS: 244234-95-5
• 化学式: C₁₆H₂₈N₂O₃
• 分子量: 296.41
• InChiKey: OUYLZKCMVGORSV-DLRWLJPMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  43.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  二碳酸二叔丁酯 、 甲基锂 、 (E)-N-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-1-(8-methyl-1,4-dioxaspiro[4.5]decan-8-yl)methanimine 在 镍 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 甲醇 为溶剂， -78.0~50.0 ℃ 、4.83 MPa 条件下， 反应 24.0h， 以57%的产率得到tert-butyl N-[(1R)-1-(8-methyl-1,4-dioxaspiro[4.5]decan-8-yl)ethyl]carbamate
  参考文献：
  名称：

  Electrophilic and Nucleophilic Reactivities of the Azomethine Carbon of SAMP-Hydrazones:  Stereoselective Synthesis of γ-Amino Ketone Derivatives

  摘要：

  A novel methodology for the asymmetric synthesis of secondary N-Boc-protected gamma-amino ketones is described. After the highly diastereoselective nucleophilic 1,4-addition of formaldehyde SAMP-hydrazone 1 to prochiral conjugated enones 2, the carbonyl group of the resulting li-oxo aldehyde SAMP-hydrazones 4 was protected as ethylene ketals 5. The stereoselective (de 58-88%) addition of organometallic reagents to the CN double bond of the latter was then performed, and the unstable intermediate hydrazines obtained were either trapped as Moc-protected hydrazines 8 in good yields (65-87%) or reduced by Raney nickel-catalyzed hydrogenolysis of the N-N bond to afford the corresponding amines, which were isolated as their corresponding N-Boc derivatives 11. Noteworthy, the azomethine carbon of SAMP-hydrazones, not being essentially modified during the process, sequentially serves as a nucleophilic and an electrophilic center, acting as a nexus between the conjugated enone (electrophile) and the organometallic reagent (nucleophile) and helping in the creation of two adjacent stereogenic centers.

  DOI：

  10.1021/jo990503r
• 作为产物：
  描述：

  乙二醇 、 在 对甲苯磺酸 作用下， 生成 (E)-N-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-1-(8-methyl-1,4-dioxaspiro[4.5]decan-8-yl)methanimine
  参考文献：
  名称：

  Electrophilic and Nucleophilic Reactivities of the Azomethine Carbon of SAMP-Hydrazones:  Stereoselective Synthesis of γ-Amino Ketone Derivatives

  摘要：

  A novel methodology for the asymmetric synthesis of secondary N-Boc-protected gamma-amino ketones is described. After the highly diastereoselective nucleophilic 1,4-addition of formaldehyde SAMP-hydrazone 1 to prochiral conjugated enones 2, the carbonyl group of the resulting li-oxo aldehyde SAMP-hydrazones 4 was protected as ethylene ketals 5. The stereoselective (de 58-88%) addition of organometallic reagents to the CN double bond of the latter was then performed, and the unstable intermediate hydrazines obtained were either trapped as Moc-protected hydrazines 8 in good yields (65-87%) or reduced by Raney nickel-catalyzed hydrogenolysis of the N-N bond to afford the corresponding amines, which were isolated as their corresponding N-Boc derivatives 11. Noteworthy, the azomethine carbon of SAMP-hydrazones, not being essentially modified during the process, sequentially serves as a nucleophilic and an electrophilic center, acting as a nexus between the conjugated enone (electrophile) and the organometallic reagent (nucleophile) and helping in the creation of two adjacent stereogenic centers.

  DOI：

  10.1021/jo990503r