tert-butyl 2-hydroxy-2-benzoylpropionate | 923569-31-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyl 2-hydroxy-2-benzoylpropionate
• 英文别名: tert-butyl (2S)-2-hydroxy-2-methyl-3-oxo-3-phenylpropanoate
• CAS: 923569-31-7
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: LOUWKPULWPRWOS-AWEZNQCLSA-N

物化性质

• 沸点：
  341.2±22.0 °C(Predicted)
• 密度：
  1.132±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  tert-butyl 2-benzoylpropionate 在 [(Pd((R)-binap)(μ-OH))2](OTf)2 、 3-苯基-2-甲苯磺酰-1,2-氧杂氮杂环丙烷 作用下， 以 二氯甲烷 为溶剂， 反应 68.0h， 生成 tert-butyl 2-hydroxy-2-benzoylpropionate 、 tert-butyl 2-hydroxy-2-benzoylpropionate
  参考文献：
  名称：

  Delineating Origins of Stereocontrol in Asymmetric Pd-Catalyzed α-Hydroxylation of 1,3-Ketoesters

  摘要：

  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.

  DOI：

  10.1021/jo1002906

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.