ethyl 2-hydroxy-2-benzoylpropionate | 1225222-64-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2-hydroxy-2-benzoylpropionate
• 英文别名: ethyl (2S)-2-hydroxy-2-methyl-3-oxo-3-phenylpropanoate
• CAS: 1225222-64-9
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: MAFHQANLQIYABF-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 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：
  63.6
• 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-3-苯基丙酸乙酯 在 3-(4-bromophenyl)-2-tosyl-1,2-oxaziridine 、 C₂₆H₂₆F₁₂N₃O⁽¹⁺⁾*I^(1-) 、 potassium carbonate 作用下， 以 甲基叔丁基醚 为溶剂， 反应 2.5h， 以42%的产率得到
  参考文献：
  名称：

  双功能铵盐同时拆分恶唑烷催化催化β-酮酸酯的不对称α-羟基氧化反应

  摘要：

  发现在无碱条件下，手性双官能含脲铵盐是β-酮酯与恶唑烷的不对称α-羟基化反应的非常有效的催化剂。该反应伴随有恶唑烷的同时动力学拆分，并且已经通过DFT计算获得了似乎可行的，迄今为止前所未有的双功能过渡态模型。

  DOI：

  10.1002/chem.201604153

文献信息

• Delineating Origins of Stereocontrol in Asymmetric Pd-Catalyzed α-Hydroxylation of 1,3-Ketoesters
  作者：Alexander M. R. Smith、Henry S. Rzepa、Andrew J. P. White、Denis Billen、King Kuok (Mimi) Hii

  DOI：10.1021/jo1002906

  日期：2010.5.7

  Systematic studies of reaction conditions and subsequent optimization led to the identification of important parameters for stereoselectivity in the asymmetric alpha-hydroxylation reaction of 1,3-ketoesters. Enantioselectivities of up to 98% can be achieved for cyclic substrates and 88% for acyclic ketoesters. Subsequently, the combination of cyclic/acyclic ketoester, catalyst, and oxidant was found to have a profound effect on reaction rates and turnover-limiting steps. The stereochemistry of the reaction contradicts that observed for other similar electrophilic substitution reactions. This was rationalized by transition-state modeling, which revealed a number of cooperative weak interactions between oxidant, ligand, and counterion, together with C-H/pi interactions that cumulatively account for the unusual stereoselectivity.
• Bifunctional Ammonium Salt Catalyzed Asymmetric α-Hydroxylation of β-Ketoesters by Simultaneous Resolution of Oxaziridines
  作者：Johanna Novacek、Joseph A. Izzo、Mathew J. Vetticatt、Mario Waser

  DOI：10.1002/chem.201604153

  日期：2016.11.21

  Chiral bifunctional urea‐containing ammonium salts were found to be very efficient catalysts for asymmetric α‐hydroxylation reactions of β‐ketoesters with oxaziridines under base‐free conditions. The reaction is accompanied by a simultaneous kinetic resolution of the oxaziridine and a plausible and so far unprecedented bifunctional transition‐state model has been obtained by means of DFT calculations

  发现在无碱条件下，手性双官能含脲铵盐是β-酮酯与恶唑烷的不对称α-羟基化反应的非常有效的催化剂。该反应伴随有恶唑烷的同时动力学拆分，并且已经通过DFT计算获得了似乎可行的，迄今为止前所未有的双功能过渡态模型。