Methyl 2--3-methylbutanoate | 164122-53-6

• 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 2--3-methylbutanoate
• 英文别名: methyl (E,S)-3-methyl-2-(4-methoxybenzylideneamino)-butyrate
• CAS: 164122-53-6
• 化学式: C₁₄H₁₉NO₃
• 分子量: 249.31
• InChiKey: YYCNNVCNRIKFMW-NCPSJORJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.31
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  47.89
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  Methyl 2--3-methylbutanoate 在 盐酸羟胺 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 (S)-2-Hydroxyamino-3-methyl-butyric acid methyl ester; hydrochloride
  参考文献：
  名称：

  Optically ActiveN-Hydroxy-α-L-Amino Acid Methyl Esters: An Improved and Simplified Synthesis

  摘要：

  本文介绍了从δ±-L-氨基酸甲酯制备光学活性 N-羟基δ-L-氨基酸甲酯的方法。该方法使用现成的起始原料，收率很高。

  DOI：

  10.1055/s-1987-28189
• 作为产物：
  描述：

  L-缬氨酸甲酯盐酸盐 、 4-甲氧基苯甲醛 在 三乙胺 4 A molecular sieve 、 四氯化钛 、 sodium sulfate 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 以96%的产率得到Methyl 2--3-methylbutanoate
  参考文献：
  名称：

  从 α-l-氨基酸甲酯高度立体选择性地合成光学纯的 C-芳基亚胺

  摘要：

  摘要 从容易获得的 α-1-氨基酸甲酯开始，标题化合物很容易合成，总产率极好。这里报告的方法的关键特征是 TiCl4 介导的 4-甲氧基苯甲醛与氨基酸衍生物的游离 α 氨基功能的缩合。该过程干净且立体选择性高，无需色谱程序即可回收相应的对映体纯手性亚胺。

  DOI：

  10.1081/scc-120026863

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。
• 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.
• Synthesis of chiral azomethines starting from L-valine methyl ester hydrochloride and substituted benzaldehydes of vanillin series
  作者：E. A. Dikusar、V. I. Potkin、N. A. Zhukovskaya

  DOI：10.1134/s1070428010050076

  日期：2010.5

  A preparative method of synthesis of chiral azomethines was developed consisting in the reaction of L-valine methyl ester hydrochloride reaction with substituted benzaldehydes of vanillin series.
• 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).
• Electroreductive Intramolecular Coupling of Chiral α-Imino Esters:  Stereoselective Synthesis of Mixed Ketals of <i>cis</i>-2,4-Disubstituted Azetidine-3-ones
  作者：Naoki Kise、Hiroshi Ozaki、Noriaki Moriyama、Yasuo Kitagishi、Nasuo Ueda

  DOI：10.1021/ja036975b

  日期：2003.9.1

  The electroreduction of chiral aromatic alpha-imino esters prepared from (S)-alpha-amino acids, such as (S)-valine, (S)-leucine, and (S)-phenylalanine, in the presence of chlorotrimethylsilane and triethylamine afforded four-membered cyclized products, mixed ketals of cis-2,4-disubstituted azetidine-3-ones, stereospecifically (>99% de, 85-99% ee). The best result of the electroreductive cyclization was obtained using BU4NClO4 as a supporting electrolyte and a Pt cathode. The absolute stereochemistry of the obtained single stereoisomers was confirmed to be 2R,3R,4S by X-ray crystallography. Calculations for the transition states of the cyclization support the stereospecific formation of the (2R,3R,4S)-isomers.