3-甲氧基-O,beta-二甲基-L-酪氨酸甲酯 | 19728-71-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3-甲氧基-O,beta-二甲基-L-酪氨酸甲酯
• 英文名称: (S)-2-amino-3-(3,4-dimethoxyphenyl)-2-methylpropanoic acid methyl ester
• 英文别名: α-methyl-β-3,4-dimethoxyphenyl-L-alanine methyl ester；Methyl 3-methoxy-O,alpha-dimethyltyrosinatato；methyl (2S)-2-amino-3-(3,4-dimethoxyphenyl)-2-methylpropanoate
• CAS: 19728-71-3
• 化学式: C₁₃H₁₉NO₄
• 分子量: 253.298
• InChiKey: PICGBRAYRQJNGT-ZDUSSCGKSA-N

物化性质

• 熔点：
  70-71 °C
• 沸点：
  120-130 °C(Press: 0.01 Torr)
• 密度：
  1.115±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  70.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-甲氧基-O,beta-二甲基-L-酪氨酸甲酯 在 氨 作用下， 以 甲醇 为溶剂， 100.0 ℃ 、506.66 kPa 条件下， 反应 168.0h， 以55%的产率得到(2S)-2-氨基-2-甲基-3-(3,4-二甲氧基苯基)丙酰胺
  参考文献：
  名称：

  Enantiocatalytic activity of substituted 5-benzyl-2-(pyridine-2-yl)imidazolidine-4-one ligands

  摘要：

  Currently, asymmetric synthesis represents one of the main streams of organic synthesis. Although an extensive research has been carried out in this area, the synthesis of chiral compounds with the required enantiomeric purity is still a challenging issue. Herein, we focus on the preparation of new enantioselective catalysts based on pyridine-imidazolidinones. The substituted 5-benzyl-2-(pyridine-2-yl)imidazolidine-4-ones 5-8 were prepared by condensation of chiral amino acid amides (alpha-methylDOPA and alpha-methylphenylalanine) with 2-acetylpyridine and pyridine-2-carbaldehyde. The individual isomers of the described ligands 5-8 were separated chromatographically. The copper(II) complexes of these chiral ligands were studied as enantioselective catalysts for the asymmetric Henry reaction of substituted aldehydes with nitromethane or nitroethane. The ligands containing a methyl group at the 2-position of the imidazolidinone ring 6a and 8a exhibit a high degree of enantioselectiyity (up to 91% ee). The nitroaldols derived from nitroethane (2-nitropropan-1-ols) were obtained with a comparable enantiomeric purity to derivatives of 2-nitroethanol. This group of ligands represents a new and promising class of enantioselective catalysts, which deserve further attention. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.02.007
• 作为产物：
  描述：

  甲基多巴 在 四氢吡咯 、 氯化亚砜 、 potassium carbonate 、 三氟乙酸 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 丙酮 为溶剂， 反应 27.0h， 生成 3-甲氧基-O,beta-二甲基-L-酪氨酸甲酯
  参考文献：
  名称：

  机械洞察不对称Ç ？烯胺催化H醛的光氧合

  摘要：

  醛在α位的有机催化光氧合反应通过烯胺催化进行，尽管烯胺应容易被单线态氧分别氧化为酰胺和羰基化合物。此外，基于实验和理论数据推测两性离子烯胺过氧化物中间体的形成。根据所用催化剂的不同，该反应可提供合适的收率（原位还原后）和（S）-或（R）-对映选择性的所需二醇。（S）-对映异构体在咪唑烷酮催化的反应中占主导地位，而脯氨酸酰胺确保了（R）立体异构体。DFT计算表明烯胺-氧复合物具有最低能量具有E， š -顺式构象的脯氨酰胺衍生物和E， š -反式的咪唑啉酮的催化剂，说明在光氧化反应的相反立体选择性。

  DOI：

  10.1002/adsc.201500056

文献信息

• New Applications of PhI(OAc)2 in Synthesis: Total Synthesis and SAR Development of Potent Antitumor Natural Product Psymberin/Irciniastatin A
  作者：Ning Shao、Xianhai Huang、Anandan Palani、Robert Aslanian、Alexei Buevich、John Piwinski、Robert Huryk、Cynthia Seidel-Dugan

  DOI：10.1055/s-0029-1216926

  日期：2009.9

  showcased in the preparation of advanced psymberin analogues. The biological data of these analogues are presented. 1 Introduction 2 Methodology Development 3 Total Synthesis of Psymberin 4 Synthesis of Psymberin Analogues: The Discovery of C11-Deoxypsymberin 5 Conclusion (diacetoxyiodo)benzene - psymberin - oxidative cycli­zation - total synthesis - antitumor

  发现了一种新颖的PhI（OAc）2介导的氧化环化反应，用于由易于合成的N-酰基烯胺以高收率合成α-氧基N-酰基缩醛和半缩醛。该方法学代表了构建天然产品pederin家族核心结构的级联过程。使用该闭环反应作为关键步骤，可完成pederin家族成员Psymberin的总合成。这种新方法在高级普西姆伯类似物的制备中得到了进一步展示。提供了这些类似物的生物学数据。 1引言 2方法论发展 3 Psymberin的全合成 4 Psymberin类似物的合成：C11-Deoxypsymberin的发现 5结论 （二乙酰氧基碘）苯-苦参素-氧化环化-全合成-抗肿瘤
• Schoellkopf; Hartwig; Pospischil, Synthesis, 1981, vol. No. 12, # 12, p. 966 - 969
  作者：Schoellkopf、Hartwig、Pospischil、Kehne

  DOI：——

  日期：——
• Asymmetrische Synthese von α-Methylaminosäure-methylestern unter Verwendung von D-Galactodialdehydals chiralem Hilfsreagens
  作者：Inga Hoppe、Ulrich Schöllkopf、Reinhold Tölle

  DOI：10.1055/s-1983-30512

  日期：——
• Enantiocatalytic activity of substituted 5-benzyl-2-(pyridine-2-yl)imidazolidine-4-one ligands
  作者：Pavel Drabina、Sergej Karel、Illia Panov、Miloš Sedlák

  DOI：10.1016/j.tetasy.2013.02.007

  日期：2013.3

  Currently, asymmetric synthesis represents one of the main streams of organic synthesis. Although an extensive research has been carried out in this area, the synthesis of chiral compounds with the required enantiomeric purity is still a challenging issue. Herein, we focus on the preparation of new enantioselective catalysts based on pyridine-imidazolidinones. The substituted 5-benzyl-2-(pyridine-2-yl)imidazolidine-4-ones 5-8 were prepared by condensation of chiral amino acid amides (alpha-methylDOPA and alpha-methylphenylalanine) with 2-acetylpyridine and pyridine-2-carbaldehyde. The individual isomers of the described ligands 5-8 were separated chromatographically. The copper(II) complexes of these chiral ligands were studied as enantioselective catalysts for the asymmetric Henry reaction of substituted aldehydes with nitromethane or nitroethane. The ligands containing a methyl group at the 2-position of the imidazolidinone ring 6a and 8a exhibit a high degree of enantioselectiyity (up to 91% ee). The nitroaldols derived from nitroethane (2-nitropropan-1-ols) were obtained with a comparable enantiomeric purity to derivatives of 2-nitroethanol. This group of ligands represents a new and promising class of enantioselective catalysts, which deserve further attention. (C) 2013 Elsevier Ltd. All rights reserved.
• Mechanistic Insights into Enantioselective CH Photooxygenation of Aldehydes<i>via</i>Enamine Catalysis
  作者：Dominika J. Walaszek、Katarzyna Rybicka-Jasińska、Sabina Smoleń、Maksymilian Karczewski、Dorota Gryko

  DOI：10.1002/adsc.201500056

  日期：2015.6.15

  aldehydes at the α‐position proceeds via enamine catalysis, though enamines should be easily oxidized by singlet oxygen respectively to amides and carbonyl compounds. Moreover, the formation of a zwitterionic enamine peroxide intermediate was postulated based on experimental and theoretical data. The reaction affords desired diols (after in situ reduction) in a decent yield and (S)‐ or (R)‐enantioselectivity

  醛在α位的有机催化光氧合反应通过烯胺催化进行，尽管烯胺应容易被单线态氧分别氧化为酰胺和羰基化合物。此外，基于实验和理论数据推测两性离子烯胺过氧化物中间体的形成。根据所用催化剂的不同，该反应可提供合适的收率（原位还原后）和（S）-或（R）-对映选择性的所需二醇。（S）-对映异构体在咪唑烷酮催化的反应中占主导地位，而脯氨酸酰胺确保了（R）立体异构体。DFT计算表明烯胺-氧复合物具有最低能量具有E， š -顺式构象的脯氨酰胺衍生物和E， š -反式的咪唑啉酮的催化剂，说明在光氧化反应的相反立体选择性。