methyl N-[1(S)-(3-pyridyl)-3-buten-1-yl]-(S)-valinate | 154228-37-2

• 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-[1(S)-(3-pyridyl)-3-buten-1-yl]-(S)-valinate
• 英文别名: methyl (2S)-3-methyl-2-[[(1S)-1-pyridin-3-ylbut-3-enyl]amino]butanoate
• CAS: 154228-37-2
• 化学式: C₁₅H₂₂N₂O₂
• 分子量: 262.352
• InChiKey: BVWGIBNEODCVBK-KBPBESRZSA-N

物化性质

• 沸点：
  362.8±42.0 °C(Predicted)
• 密度：
  1.023±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  51.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl N-[1(S)-(3-pyridyl)-3-buten-1-yl]-(S)-valinate 在 lithium aluminium tetrahydride 、 高碘酸 、 甲胺 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 1.0h， 生成 (1S)-1-(3-吡啶基)-3-丁烯-1-胺
  参考文献：
  名称：

  Asymmetric Synthesis of δ-Substituted α,β-Unsaturated δ-Lactams by Ring Closing Metathesis of Enantiomerically Pure N-Acryloyl-homoallylic Amines

  摘要：

  Optically pure secondary homoallylic amines, obtained by highly diastereoselective addition of allylmetal reagents to imines derived from chiral amines, were N-dealkylated, and the primary amines were converted to N-acryloyl amides. Then, ring closing metathesis gave delta-substituted delta-lactams in good overall yields.

  DOI：

  10.1021/jo0703000
• 作为产物：
  描述：

  3-吡啶甲醛 在 magnesium sulfate 、 三乙胺 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 51.0h， 生成 methyl N-[1(S)-(3-pyridyl)-3-buten-1-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

• Enantioselective synthesis of homoallylic amines. Evidence of reversible addition of allylzinc bromide to aromatic imines derived from (S)-valine methyl ester and (S)-valinol
  作者：Allaye Bocoum、Diego Savoia、Achille Umani-Ronchi

  DOI：10.1039/c39930001542

  日期：——

  The reaction of aromatic and aliphatic imines derived from (S)-valine methyl ester and (S)-valinol with allyl bromide and zinc in tetrahydrofuran affords homoallylic amines with up to 100% diastereoisomeric excess (d.e.), but in the case of the aromatic imines the diastereoselectivity is lowered by increasing the reaction time, owing to the reversibility of the allylation reaction.

  由(S)-缬氨酸甲酯和(S)-缬氨醇衍生的芳香族和脂肪族亚胺与椰基溴和锌在四氢呋喃中反应，生成具有高达100%差异异构体过量（d.e.）的同烯丙胺，但在芳香族亚胺的情况下，随着反应时间的增加，差异选择性降低，这是由于烯丙基化反应的可逆性所致。
• A highly stereoselective one-pot asymmetric synthesis of homoallylic amines and amino acids from aldehydes
  作者：Teck-Peng Loh、Diana Sook-Chiang Ho、Kai-Chen Xu、Keng-Yeow Sim

  DOI：10.1016/s0040-4039(96)02427-6

  日期：1997.2

  A simple and efficient one-pot method was developed to give chiral homoallylic amines and amino acids from the respective aldehydes in high stereoselectivity.

  开发了一种简单有效的一锅法，以高立体选择性从相应的醛中得到手性均烯丙基胺和氨基酸。
• Asymmetric Synthesis of δ-Substituted α,β-Unsaturated δ-Lactams by Ring Closing Metathesis of Enantiomerically Pure <i>N</i>-Acryloyl-homoallylic Amines
  作者：Claudio Fiorelli、Diego Savoia

  DOI：10.1021/jo0703000

  日期：2007.8.1

  Optically pure secondary homoallylic amines, obtained by highly diastereoselective addition of allylmetal reagents to imines derived from chiral amines, were N-dealkylated, and the primary amines were converted to N-acryloyl amides. Then, ring closing metathesis gave delta-substituted delta-lactams in good overall yields.
• 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).