(E)-N-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-1-[(8R)-8-methyl-1,4-dioxaspiro[4.4]nonan-8-yl]methanimine | 244234-91-1

• 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-[(8R)-8-methyl-1,4-dioxaspiro[4.4]nonan-8-yl]methanimine
• CAS: 244234-91-1
• 化学式: C₁₅H₂₆N₂O₃
• 分子量: 282.383
• InChiKey: RBZOELQWHOWRBS-AXAJZXMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  甲基锂 、 (E)-N-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-1-[(8R)-8-methyl-1,4-dioxaspiro[4.4]nonan-8-yl]methanimine 以 四氢呋喃 、 乙醚 为溶剂， 以62%的产率得到(2S)-2-(methoxymethyl)-N-[(1R)-1-[(8R)-8-methyl-1,4-dioxaspiro[4.4]nonan-8-yl]ethyl]pyrrolidin-1-amine
  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 、 (3R)-3-[(E)-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]iminomethyl]-3-methylcyclopentan-1-one 在 对甲苯磺酸 作用下， 生成 (E)-N-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]-1-[(8R)-8-methyl-1,4-dioxaspiro[4.4]nonan-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

文献信息

• Electrophilic and Nucleophilic Reactivities of the Azomethine Carbon of SAMP-Hydrazones:  Stereoselective Synthesis of γ-Amino Ketone Derivatives
  作者：Dieter Enders、Elena Díez、Rosario Fernández、Eloísa Martín-Zamora、Jesús M. Muñoz、Rafael R. Pappalardo、José M. Lassaletta

  DOI：10.1021/jo990503r

  日期：1999.8.1

  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.