Methyl N-<(4S)-1-nonen-4-yl>-(S)-valinate | 134304-83-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Methyl N-<(4S)-1-nonen-4-yl>-(S)-valinate
• 英文别名: methyl (2S)-3-methyl-2-[[(4S)-non-1-en-4-yl]amino]butanoate
• CAS: 134304-83-9
• 化学式: C₁₅H₂₉NO₂
• 分子量: 255.401
• InChiKey: FIVJDRIYPUEKSI-KGLIPLIRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  18
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  L-缬氨酸甲酯盐酸盐 在 magnesium sulfate 、 三乙胺 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 Methyl N-<(4S)-1-nonen-4-yl>-(S)-valinate
  参考文献：
  名称：

  Enantioselective Synthesis of Homoallylic Amines by Addition of Allylmetal Reagents to Imines Derived from (S)-Valine Esters

  摘要：

  Grignard and Barbier procedures have been applied to the addition of allylmetal (Zn, Cu, Pb, Bi, Al, In) species to imines derived from (S)-valine esters, principally the methyl ester. The Zn-mediated, CeCl3- or SnCl2-catalyzed ''Barbier'' reactions of the imines with allyl bromide in THF in Ar atmosphere at room temperature proved particularly convenient, efficient and selective, providing the secondary homoallylic amines with excellent to perfect diastereoselectivity. The si face of the imine was attacked preferentially in every case. The addition of allylzinc bromide to aromatic imines was affected by reversibility, which caused the lowering of the diastereoisomeric ratio with increasing the reaction time. However, the retroallylation reaction could be avoided by performing the reaction in the presence of trace amounts of water, or by using CeCl3.7H(2)O as the catalyst, although at the expense of the reaction rate. The bimetal redox systems Al-PbBr2, -SnCl2, -TiCl4, and -BiCl3 were applied to the allylation of the imines derived from methyl valinate, but satisfactory results were achieved only with Al-BiCl3 and -TiCl4 systems. However, the use of the Al(Hg) and Al-PbBr2 system afforded almost perfect chemo- and diastereoselectivity on the benzaldehyde imine derived from tert-butyl (S)-valinate. The synthesis of (S)-1-phenyl-3-butenamine from the corresponding secondary homoallylic amine was accomplished by a two-step sequence, consisting of the controlled reduction of the methyl ester with LiAlH4 and subsequent oxidative cleavage with H5IO6-MeNH(2).

  DOI：

  10.1021/jo00104a037

文献信息

• Diastereoselective allylation of chiral imines. Novel application of allylcopper reagents to the enantioselective synthesis of homoallyl amines
  作者：Allaye Bocoum、Carla Boga、Diego Savoia、Achille Umani-Ronchi

  DOI：10.1016/s0040-4039(00)79669-9

  日期：1991.3

  The addition of allylcopper reagents to imines derived from S-valine occurs with excellent diastereoselectivity (e.e. 98 %).

  将烯丙基铜试剂添加到衍生自S-缬氨酸的亚胺中时，非对映选择性极好（ee 98％）。
• Enantioselective Synthesis of Homoallylic Amines by Addition of Allylmetal Reagents to Imines Derived from (S)-Valine Esters
  作者：Tiziana Basile、Allaye Bocoum、Diego Savoia、Achille Umani-Ronchi

  DOI：10.1021/jo00104a037

  日期：1994.12

  Grignard and Barbier procedures have been applied to the addition of allylmetal (Zn, Cu, Pb, Bi, Al, In) species to imines derived from (S)-valine esters, principally the methyl ester. The Zn-mediated, CeCl3- or SnCl2-catalyzed ''Barbier'' reactions of the imines with allyl bromide in THF in Ar atmosphere at room temperature proved particularly convenient, efficient and selective, providing the secondary homoallylic amines with excellent to perfect diastereoselectivity. The si face of the imine was attacked preferentially in every case. The addition of allylzinc bromide to aromatic imines was affected by reversibility, which caused the lowering of the diastereoisomeric ratio with increasing the reaction time. However, the retroallylation reaction could be avoided by performing the reaction in the presence of trace amounts of water, or by using CeCl3.7H(2)O as the catalyst, although at the expense of the reaction rate. The bimetal redox systems Al-PbBr2, -SnCl2, -TiCl4, and -BiCl3 were applied to the allylation of the imines derived from methyl valinate, but satisfactory results were achieved only with Al-BiCl3 and -TiCl4 systems. However, the use of the Al(Hg) and Al-PbBr2 system afforded almost perfect chemo- and diastereoselectivity on the benzaldehyde imine derived from tert-butyl (S)-valinate. The synthesis of (S)-1-phenyl-3-butenamine from the corresponding secondary homoallylic amine was accomplished by a two-step sequence, consisting of the controlled reduction of the methyl ester with LiAlH4 and subsequent oxidative cleavage with H5IO6-MeNH(2).