methyl N-[(4R)-4-phenylbut-1-en-4-yl]-(S)-valinate | 130518-00-2

• 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-[(4R)-4-phenylbut-1-en-4-yl]-(S)-valinate
• 英文别名: methyl (2S)-3-methyl-2-[[(1R)-1-phenylbut-3-enyl]amino]butanoate
• CAS: 130518-00-2
• 化学式: C₁₆H₂₃NO₂
• 分子量: 261.364
• InChiKey: NKXLAUVDDSIQGA-CABCVRRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.09
• 重原子数：
  19.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  38.33
• 氢给体数：
  1.0
• 氢受体数：
  3.0

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 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 methyl N-[(4R)-4-phenylbut-1-en-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

• 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。
• 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％）。
• A novel “Ti(O)” induced allylation of imines in a TiCl4 (cat.)/A1 bimetal system. Chirality transfer of l-valine to homoallylamine
  作者：Hideo Tanaka、Keizo Inoue、Ulrike Pokorski、Masatoshi Taniguchi、Sigeru Torii

  DOI：10.1016/s0040-4039(00)89015-2

  日期：——

  “Barbier Type” allylation of imines with allyl bromide has been performed successfully by the action of aluminum (1 equiv.) and titanium(IV)chloride (0.05 equiv.) in THF. The chirality transfer of α-amino acid esters to homoallyl amines is demonstrated by allylation of N-benzalvaline methyl ester followed by alkaline hydrolysis and electrolytic decarboxylation.

  亚胺与烯丙基溴的“ Barbier型”烯丙基化已经成功地通过铝（1当量）和氯化钛（IV）（THF当量）在THF中的作用完成。α-氨基酸酯向均烯丙基胺的手性转移通过N-苯并缬氨酸甲酯的烯丙基化，然后进行碱水解和电解脱羧来证明。
• A modification of the Hiyama reaction. Synthesis of homo allylic amines from imines and allylic bromides in the presence of CrCl2
  作者：Maria Giammaruco、Maurizio Taddei、Paola Ulivi

  DOI：10.1016/s0040-4039(00)73656-2

  日期：1993.5

  Arylic and alkylic imines, activated with BF3-OEt2 react with different allylic bromides in the presence of CrCl2 to give the corresponding homo allylic amines. The reaction can be performed in a single step starting from the aldehyde and the amine, in the presence of molecular sieves (4 Å), in a sort of amino-allylation of aldehydes. With the imine derived from benzaldehyde and (S)-valine a good diastereomeric

  在CrCl 2的存在下，被BF 3 -OEt 2活化的丙烯酸和烷基亚胺与不同的丙烯酸烯丙酯反应，得到相应的均烯丙基胺。该反应可以在醛类的氨基烯丙基化的情况下，在分子筛（4Å）存在的情况下，从醛和胺开始的单一步骤中进行。用衍生自苯甲醛和（S）-缬氨酸的亚胺，可获得良好的非对映异构体过量（86％）。
• Preparation of Both Diastereomers of Homoallylic Amines by Allylmetalation of Methyl <i>N</i>-Benzylidene-(<i>S</i>)-valinate
  作者：Ashraf A. El-Shehawy、Mahmoud A. Omara、Koichi Ito、Shinichi Itsuno

  DOI：10.1055/s-1998-1681

  日期：1998.4

  The reaction of enantiopure imine 1 with methallyl or prenylzinc reagents affords homoallylic amines having (S,S) configuration with up to 100% diastereomeric excess. Another diastereomer, (R,S)-amines, is obtained from the same imine 1 by using allylboron reagents.

  手性纯烯胺1与甲基丙烯基或普伦基锌试剂的反应生成具有(S,S)构型的同伴胺，反应的二级立体化合物过量可达100%。另一种二级立体异构体(R,S)-胺则是通过使用烯基硼试剂从同一烯胺1获得的。