t-butyl 2-amino-2-methyl-3-oxobutanoate | 1381800-96-9

• 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: t-butyl 2-amino-2-methyl-3-oxobutanoate
• 英文别名: tert-butyl (2R)-2-amino-2-methyl-3-oxobutanoate
• CAS: 1381800-96-9
• 化学式: C₉H₁₇NO₃
• 分子量: 187.239
• InChiKey: KDPBLZWMGBUSHJ-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  69.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-甲基-3-氧代丁酸叔丁酯 在 N-氯代丁二酰亚胺 、 sodium azide 、 10 % Pd-BaSO4 、 C₃₄H₂₄N₂O 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 甲醇 、 二甲基亚砜 、 苯 为溶剂， 反应 1.0h， 生成 t-butyl 2-amino-2-methyl-3-oxobutanoate
  参考文献：
  名称：

  Highly Enantioselective Chlorination of β-Keto Esters and Subsequent S_N2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers

  摘要：

  Highly enantioselective chlorination of beta-oxo esters and subsequent stereospecific substitution of tertiary chlorides are described. Enantioselective chlorination of beta-keto esters and malonates was performed using a chiral Lewis acid catalyst prepared from Cu(OTf)(2) and the newly developed spirooxazoline ligand 2 to yield the desired a-chlorinated products with high enantioselectivity (up to 98% ee). Nucleophilic substitution of the resulting chlorides proceeded smoothly to afford a variety of chiral molecules such as alpha-amino, alpha-allcylthio, and alpha-fluoro esters, without loss of enantiopurity. The results of X-ray crystallographic analysis proved that Walden inversion occurs at the chlorinated tertiary carbon center. These results supported the fact that the substitution proceeds via an S(N)2 mechanism.

  DOI：

  10.1021/ja304806j

文献信息

• Merging Aerobic Oxidation and Enamine Catalysis in the Asymmetric α-Amination of β-Ketocarbonyls Using<i>N</i>-Hydroxycarbamates as Nitrogen Sources
  作者：Changming Xu、Long Zhang、Sanzhong Luo

  DOI：10.1002/anie.201400776

  日期：2014.4.14

  We describe herein an unprecedented asymmetric α‐amination of β‐ketocarbonyls under aerobic conditions. The process is enabled by a simple chiral primary amine through the coupling of a catalytic enamine ester intermediate and a nitrosocarbonyl (generated in situ) derived from N‐hydroxycarbamate. The reaction features high chemoselectivity and excellent enantioselectivity for a broad range of substrates

  我们在本文中描述了有氧条件下前所未有的β-酮羰基α-不对称α-胺化反应。一个简单的手性伯胺通过催化烯胺酯中间体与衍生自N-羟基氨基甲酸酯的亚硝基羰基化合物（原位生成）的偶联来实现该过程。该反应对多种底物具有高化学选择性和出色的对映选择性。
• Highly Enantioselective Chlorination of β-Keto Esters and Subsequent S_N2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers
  作者：Kazutaka Shibatomi、Yoshinori Soga、Akira Narayama、Ikuhide Fujisawa、Seiji Iwasa

  DOI：10.1021/ja304806j

  日期：2012.6.20

  Highly enantioselective chlorination of beta-oxo esters and subsequent stereospecific substitution of tertiary chlorides are described. Enantioselective chlorination of beta-keto esters and malonates was performed using a chiral Lewis acid catalyst prepared from Cu(OTf)(2) and the newly developed spirooxazoline ligand 2 to yield the desired a-chlorinated products with high enantioselectivity (up to 98% ee). Nucleophilic substitution of the resulting chlorides proceeded smoothly to afford a variety of chiral molecules such as alpha-amino, alpha-allcylthio, and alpha-fluoro esters, without loss of enantiopurity. The results of X-ray crystallographic analysis proved that Walden inversion occurs at the chlorinated tertiary carbon center. These results supported the fact that the substitution proceeds via an S(N)2 mechanism.