ethyl 3-amino-3-oxo-2-(thiophen-3-yl)propanoate | 1190830-42-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3-amino-3-oxo-2-(thiophen-3-yl)propanoate
• 英文别名: Ethyl 3-amino-3-oxo-2-thiophen-3-ylpropanoate
• CAS: 1190830-42-2
• 化学式: C₉H₁₁NO₃S
• 分子量: 213.257
• InChiKey: NDXDQGLBRLEUHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  97.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  偶氮二甲酸二叔丁酯 、 ethyl 3-amino-3-oxo-2-(thiophen-3-yl)propanoate 在 (R)-N-(2-hydroxyphenyl)-2-(2-hydroxybenzoylamino)-3-methylbutylamide 、 lanthanum(III) nitrate hexahydrate 、 D-valine t-butyl ester 作用下， 以 乙酸乙酯 为溶剂， 反应 15.0h， 以99%的产率得到(R)-di-tert-butyl 1-(1-amino-3-ethoxy-1,3-dioxo-2-(thiophen-3-yl)propan-2-yl)hydrazine-1,2-dicarboxylate
  参考文献：
  名称：

  Managing Highly Coordinative Substrates in Asymmetric Catalysis: A Catalytic Asymmetric Amination with a Lanthanum-Based Ternary Catalyst

  摘要：

  Full details of a catalytic asymmetric amination with a lanthanum/amide-based ligand catalyst system are described. A catalyst comprising La(NO3)(3)center dot 6H(2)O, (R)-3a and H-D-Val-V'Bu was identified to promote the catalytic asymmetric amination of nonprotected succinimide derivative 1 with as little as 1 mol % catalyst loading Mechanistic studies by various spectroscopic analyses and several control and kinetic experiments suggested that the catalyst components were in equilibrium between the associated and dissociated forms, and that the reaction likely proceeded through a La(NO3)(3)center dot 6H(2)O/(R)-3a/H-D-Val-O'Bu ternary complex. This catalyst system was also effective for asymmetric amination of N-nonsubstituted alpha-alkoxycarbonyl amides 7, hitherto unprecedented substrates in asymmetric catalysis, probably due to their attenuated reactivity and difficult stereocontrol, affording the amination products in up to > 99% yield and > 99% ee. The high catalytic performance and enantiocontrol of the reaction with highly coordinative substrates were achieved by the activation/recognition of the substrates exerted by coordination to lanthanum and hydrogen bonding cooperatively in the transition state.

  DOI：

  10.1021/ja9052653
• 作为产物：
  描述：

  2-氰基-2-(3-噻吩基)乙酸乙酯 在 盐酸 作用下， 以 甲酸 为溶剂， 生成 ethyl 3-amino-3-oxo-2-(thiophen-3-yl)propanoate
  参考文献：
  名称：

  Managing Highly Coordinative Substrates in Asymmetric Catalysis: A Catalytic Asymmetric Amination with a Lanthanum-Based Ternary Catalyst

  摘要：

  Full details of a catalytic asymmetric amination with a lanthanum/amide-based ligand catalyst system are described. A catalyst comprising La(NO3)(3)center dot 6H(2)O, (R)-3a and H-D-Val-V'Bu was identified to promote the catalytic asymmetric amination of nonprotected succinimide derivative 1 with as little as 1 mol % catalyst loading Mechanistic studies by various spectroscopic analyses and several control and kinetic experiments suggested that the catalyst components were in equilibrium between the associated and dissociated forms, and that the reaction likely proceeded through a La(NO3)(3)center dot 6H(2)O/(R)-3a/H-D-Val-O'Bu ternary complex. This catalyst system was also effective for asymmetric amination of N-nonsubstituted alpha-alkoxycarbonyl amides 7, hitherto unprecedented substrates in asymmetric catalysis, probably due to their attenuated reactivity and difficult stereocontrol, affording the amination products in up to > 99% yield and > 99% ee. The high catalytic performance and enantiocontrol of the reaction with highly coordinative substrates were achieved by the activation/recognition of the substrates exerted by coordination to lanthanum and hydrogen bonding cooperatively in the transition state.

  DOI：

  10.1021/ja9052653

文献信息

• Catalytic asymmetric hydroxylation of α-alkoxycarbonyl amides with a Pr(OiPr)3/amide-based ligand catalyst
  作者：Sho Takechi、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1016/j.tetlet.2010.11.064

  日期：2011.4

  A catalytic asymmetric hydroxylation of N-nonsubstituted alpha-alkoxycarbonyl amides is described. A new effective catalyst comprising Pr((OPr)-Pr-i)(3) and a fluoro-substituted amide-based ligand was identified using oxaziridine as the oxidizing reagent. The catalyst components were in dynamic equilibrium in the reaction mixture, which assembled to form the associated transition state through metal coordination and hydrogen bonding. (C) 2010 Elsevier Ltd. All rights reserved.
• Managing Highly Coordinative Substrates in Asymmetric Catalysis: A Catalytic Asymmetric Amination with a Lanthanum-Based Ternary Catalyst
  作者：Tomoyuki Mashiko、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1021/ja9052653

  日期：2009.10.21

  Full details of a catalytic asymmetric amination with a lanthanum/amide-based ligand catalyst system are described. A catalyst comprising La(NO3)(3)center dot 6H(2)O, (R)-3a and H-D-Val-V'Bu was identified to promote the catalytic asymmetric amination of nonprotected succinimide derivative 1 with as little as 1 mol % catalyst loading Mechanistic studies by various spectroscopic analyses and several control and kinetic experiments suggested that the catalyst components were in equilibrium between the associated and dissociated forms, and that the reaction likely proceeded through a La(NO3)(3)center dot 6H(2)O/(R)-3a/H-D-Val-O'Bu ternary complex. This catalyst system was also effective for asymmetric amination of N-nonsubstituted alpha-alkoxycarbonyl amides 7, hitherto unprecedented substrates in asymmetric catalysis, probably due to their attenuated reactivity and difficult stereocontrol, affording the amination products in up to > 99% yield and > 99% ee. The high catalytic performance and enantiocontrol of the reaction with highly coordinative substrates were achieved by the activation/recognition of the substrates exerted by coordination to lanthanum and hydrogen bonding cooperatively in the transition state.