N'-[1-((3aS,7aS)-1,3-Dimethyl-octahydro-benzoimidazol-2-yl)-ethyl]-N,N-dimethyl-hydrazine | 133643-22-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 亚胺内酰胺
• 英文名称: N'-[1-((3aS,7aS)-1,3-Dimethyl-octahydro-benzoimidazol-2-yl)-ethyl]-N,N-dimethyl-hydrazine
• CAS: 133643-22-8
• 化学式: C₁₃H₂₈N₄
• 分子量: 240.392
• InChiKey: DIGWYHBXDMULDN-RAMGSTBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.96
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  21.75
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  (1S,2S)-(+)-N,N'-二甲基环己烷-1,2-二胺 以 四氢呋喃 为溶剂， 生成 N'-[1-((3aS,7aS)-1,3-Dimethyl-octahydro-benzoimidazol-2-yl)-ethyl]-N,N-dimethyl-hydrazine
  参考文献：
  名称：

  Chiral aminal termplates 61. Diastereoselectivity of hydrazone alkylation. Asymmetric synthesis of α-aminoaldehydes

  摘要：

  Glyoxal is efficiently transformed into the chiral aminals bearing the hydrazone functionality 2a and 2b. These compounds react under complete diastereocontrol with various organolithium reagents, affording chiral hydrazines 3-9. Reduction with Raney nickel leads to aminal protected alpha-aminoaldehydes, which, in turn, are easily hydrolyzed to the free chiral aldehydes (after tBoc protection of the amine).

  DOI：

  10.1016/s0040-4039(00)92036-7

文献信息

• Chiral Aminal Templates: Diastereoselective Addition to Hydrazones; An Asymmetric Synthesis of α-Amino Aldehydes
  作者：Alex Alexakis、Nathalie Lensen、Jean-Philippe Tranchier、Pierre Mangeney、J. Feneau-Dupont、J. P. Declercq

  DOI：10.1055/s-1995-4042

  日期：1995.8

  The monohydrazone of glyoxal may be derivatized into a chiral aminal with diamine 7. The resulting chiral reagent 13 reacts with complete diastereocontrol with organolithium reagents in THF. This sterically controlled reaction may be altered to chelation control by using Grignard reagents in toluene, affording the opposite diastereomer in excellent de. The N-N bond of the hydrazine functionality is then cleaved with Raney nickel, assisted by ultrasound. After protection of the resulting primary amino functionality, the aminal is hydrolyzed to afford the desired α-amino aldehydes without epimerization. The same reaction sequence, without cleavage of the N-N bond, affords an α-hydrazino aldehyde.

  乙二醛的单氢肼可与二胺7衍生化为一个手性氨胺。所得的手性试剂13在四氢呋喃中与有机锂试剂反应，具有完全的非对映体选择性。通过在甲苯中使用格氏试剂，这一立体控制反应可被改变为螯合控制，从而生成相反的非对映体，并获得优异的对映选择性。接着，利用超声波的辅助下，水合肼的N-N键被拉尼镍裂解。在保护产物中的初级氨基功能基后，氨胺被水解，生成所需的α-氨基醛而不发生表异构化。相同的反应序列，如果不裂解N-N键，则会生成α-肼醛。