Triethylsilyl 4-acetylbenzoate | 1215225-75-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Triethylsilyl 4-acetylbenzoate
• 英文别名: triethylsilyl 4-acetylbenzoate
• CAS: 1215225-75-4
• 化学式: C₁₅H₂₂O₃Si
• 分子量: 278.423
• InChiKey: LXJIEVZTWCYYFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  三乙基硅烷 、 4-乙酰基苯甲酸 在 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 作用下， 以 1,4-二氧六环 为溶剂， 反应 7.0h， 以90%的产率得到Triethylsilyl 4-acetylbenzoate
  参考文献：
  名称：

  甲硅烷基酯和甲硅烷基醚的高效无溶剂路线

  摘要：

  Abstractmagnified imageDinuclear metal complexes, especially (p‐cymene)ruthenium dichloride dimer {[RuCl2(p‐cymene)]2}, have been found to exhibit high catalytic performance for the dehydrosilylation of various kinds of carboxylic acids and alcohols. The dehydrosilylation with [RuCl2(p‐cymene)]2 proceeded efficiently with only one equivalent of silane with respect to substrate (carboxylic acids or alcohols) under solvent‐free conditions to give the corresponding silyl esters and ethers in excellent yields with a high turnover number (TON) and frequency (TOF). The 1H NMR spectrum of a toluene‐d8 solution of [RuCl2(p‐cymene)]2 and a silane showed a signal assignable to the ruthenium hydride species. In contrast, no new signals were detected in the 1H NMR spectrum of a toluene‐d8 solution of [RuCl2(p‐cymene)]2 and a carboxylic acid or an alcohol. Therefore, the ruthenium metal in [RuCl2(p‐cymene)]2 activates a silane to afford the hydride intermediate, possibly a silylmetal hydride species. Then, the nucleophilic attack of a substrate (carboxylic acid or alcohol) to the hydride intermediate proceeds to give the corresponding silylated product. The present dehydrosilylation with an optically active silane proceeded exclusively under inversion of stereochemistry at the chiral silicon center, suggesting that the nucleophilic attack of a substrate to the hydride intermediate occurs from the backside of the ruthenium‐silicon bond.

  DOI：

  10.1002/adsc.200900230

文献信息

• An Efficient Solvent-Free Route to Silyl Esters and Silyl Ethers
  作者：Yuko Ojima、Kazuya Yamaguchi、Noritaka Mizuno

  DOI：10.1002/adsc.200900230

  日期：2009.6

  Abstractmagnified imageDinuclear metal complexes, especially (p‐cymene)ruthenium dichloride dimer [RuCl2(p‐cymene)]2}, have been found to exhibit high catalytic performance for the dehydrosilylation of various kinds of carboxylic acids and alcohols. The dehydrosilylation with [RuCl2(p‐cymene)]2 proceeded efficiently with only one equivalent of silane with respect to substrate (carboxylic acids or alcohols) under solvent‐free conditions to give the corresponding silyl esters and ethers in excellent yields with a high turnover number (TON) and frequency (TOF). The 1H NMR spectrum of a toluene‐d8 solution of [RuCl2(p‐cymene)]2 and a silane showed a signal assignable to the ruthenium hydride species. In contrast, no new signals were detected in the 1H NMR spectrum of a toluene‐d8 solution of [RuCl2(p‐cymene)]2 and a carboxylic acid or an alcohol. Therefore, the ruthenium metal in [RuCl2(p‐cymene)]2 activates a silane to afford the hydride intermediate, possibly a silylmetal hydride species. Then, the nucleophilic attack of a substrate (carboxylic acid or alcohol) to the hydride intermediate proceeds to give the corresponding silylated product. The present dehydrosilylation with an optically active silane proceeded exclusively under inversion of stereochemistry at the chiral silicon center, suggesting that the nucleophilic attack of a substrate to the hydride intermediate occurs from the backside of the ruthenium‐silicon bond.