(2-Phenyl-2-trimethylsilyloxyethyl) benzoate | 128733-28-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2-Phenyl-2-trimethylsilyloxyethyl) benzoate
• CAS: 128733-28-8
• 化学式: C₁₈H₂₂O₃Si
• 分子量: 314.456
• InChiKey: GLRWIPPCOVWISI-UHFFFAOYSA-N

物化性质

• 沸点：
  386.9±35.0 °C(Predicted)
• 密度：
  1.059±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.44
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  苯甲酰溴 、 2,2-di-n-Butyl-4-phenyl-1,3,2-dioxastannole 以 氘代氯仿 为溶剂， 生成 2-hydroxy-2-phenylethyl benzoate 、 2-hydroxy-1-phenylethyl benzoate 、 (2-Phenyl-2-trimethylsilyloxyethyl) benzoate 、 Benzoic acid 1-phenyl-2-trimethylsilanyloxy-ethyl ester
  参考文献：
  名称：

  Organotin-Mediated Monoacylation of Diols with Reversed Chemoselectivity. Mechanism and Selectivity¹

  摘要：

  The monoesterification of unsymmetrically substituted diols, which occurs at the most substituted hydroxyl when activation of the substrate is achieved through its dibutylstannylene acetal, has been investigated to ascertain the origin of the unusual reversal of chemoselectivity. A mechanism in which the dibutylstannylene acetal plays the double role of reagent and catalyst has been established, which accounts for the reactivity, selectivity, and product distribution of the reaction, The reaction pathway involves three subsequent steps, namely, (a) esterification, (b) intra- and intermolecular transesterification, and (c) quench; interplay between kinetic and thermodynamic control over the three steps is responsible for the observed product distribution. The knowledge of the reaction mechanism allows for adjustment of experimental conditions to achieve optimum selectivity, which can be >99% with the appropriate choice of reagents. The stannylation procedure converts hydroxyls into functional groups highly chemoselective toward acyl reagents, but inert toward sulfonyl halides and alkylating reagents. The reactivity of the Sn-O bond has been found to decrease with decreasing the electronegativity of ligands on tin, while halide ligands appear to be essential for reversal of chemoselectivity. A structure has been proposed for the catalytic species, in which complexation of the stannyl monoester intermediates with the starting dioxastannolane reagent activates the stannylated oxygen toward addition to the carbonyl and at the same time accounts for the steric hindrance that biases the intramolecular transesterification equilibrium toward the thermodynamically most stable monoester of the most substituted hydroxyl.

  DOI：

  10.1021/jo960453f

文献信息

• Group 14 organometallic reagents. 9. Organotin-mediated monoacylation of diols with reversed chemoselectivity: a convenient synthetic method
  作者：Gianna Reginato、Alfredo Ricci、Stefano Roelens、Serena Scapecchi

  DOI：10.1021/jo00304a027

  日期：1990.8
• Organotin-Mediated Monoacylation of Diols with Reversed Chemoselectivity. Mechanism and Selectivity¹
  作者：Stefano Roelens

  DOI：10.1021/jo960453f

  日期：1996.1.1

  The monoesterification of unsymmetrically substituted diols, which occurs at the most substituted hydroxyl when activation of the substrate is achieved through its dibutylstannylene acetal, has been investigated to ascertain the origin of the unusual reversal of chemoselectivity. A mechanism in which the dibutylstannylene acetal plays the double role of reagent and catalyst has been established, which accounts for the reactivity, selectivity, and product distribution of the reaction, The reaction pathway involves three subsequent steps, namely, (a) esterification, (b) intra- and intermolecular transesterification, and (c) quench; interplay between kinetic and thermodynamic control over the three steps is responsible for the observed product distribution. The knowledge of the reaction mechanism allows for adjustment of experimental conditions to achieve optimum selectivity, which can be >99% with the appropriate choice of reagents. The stannylation procedure converts hydroxyls into functional groups highly chemoselective toward acyl reagents, but inert toward sulfonyl halides and alkylating reagents. The reactivity of the Sn-O bond has been found to decrease with decreasing the electronegativity of ligands on tin, while halide ligands appear to be essential for reversal of chemoselectivity. A structure has been proposed for the catalytic species, in which complexation of the stannyl monoester intermediates with the starting dioxastannolane reagent activates the stannylated oxygen toward addition to the carbonyl and at the same time accounts for the steric hindrance that biases the intramolecular transesterification equilibrium toward the thermodynamically most stable monoester of the most substituted hydroxyl.