dimethyl(phenyl)silyl benzoate | 53358-43-3

• 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: dimethyl(phenyl)silyl benzoate
• 英文别名: Benzoesaeure-(dimethylphenylsilyl)-ester；PhCOOSiMe2Ph；[dimethyl(phenyl)silyl] benzoate
• CAS: 53358-43-3
• 化学式: C₁₅H₁₆O₂Si
• 分子量: 256.376
• InChiKey: GQILZMASDATCMN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.96
• 重原子数：
  18.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  (dimethyl(phenyl)silyl)(phenyl)methanone 生成 dimethyl(phenyl)silyl benzoate
  参考文献：
  名称：

  SEKIGUCHI AKIRA; KABE YOSHIO; ANDO WATARU, TETRAHEDRON LETT., 1979, NO 10, 871-872

  摘要：

  DOI：

文献信息

• Rhodium Carbene Complexes as Versatile Catalyst Precursors for SiH Bond Activation
  作者：Anneke Krüger、Martin Albrecht

  DOI：10.1002/chem.201102197

  日期：2012.1.9

  Rhodium(III) complexes comprising monoanionic C,C,C‐tridentate dicarbene ligands activate SiH bonds and catalyse the hydrolysis of hydrosilanes to form silanols and siloxanes with concomitant release of H2. In dry MeNO2, selective formation of siloxanes takes place, while changing conditions to wet THF produces silanols exclusively. Silyl ethers are formed when ROH is used as substrate, thus providing

  包括单阴离子Ç铑（III）络合物，C，C-三齿配体dicarbene激活的Si  H键和催化氢硅烷的水解以形成硅烷醇和硅氧烷的H伴随释放2。在干燥的MeNO 2中，会选择性地形成硅氧烷，而改变条件以使湿THF专门产生硅烷醇。当将ROH用作底物时会形成甲硅烷基醚，因此为保护以H 2为唯一副产物的醇提供了一条温和的途径。对于炔烃，发生相当快速的氢化硅烷化，而羰基不受影响。Si的进一步扩展H键活化成二氢硅烷得到硅酮和聚甲硅烷基醚。使用氘代硅烷的机理研究表明氘掺入了异常的卡宾配体中，因此表明了涉及杂化SiH键裂解的配体辅助机制。
• Cationic Silane σ-Complexes of Ruthenium with Relevance to Catalysis
  作者：Dmitry V. Gutsulyak、Sergei F. Vyboishchikov、Georgii I. Nikonov

  DOI：10.1021/ja101583m

  日期：2010.5.5

  Hydrositylation of carbonyls catalyzed by 2 goes via intermediate formation of cationic silane sigma-complexes 4 which undergo nucleophilic abstraction of the silylium cation studied by DFT calculations.
• Chemoselective Ruthenium-Catalysed Reduction of Carboxylic Acids
  作者：José A. Fernández-Salas、Simone Manzini、Steven P. Nolan

  DOI：10.1002/adsc.201301088

  日期：2014.2.10

  AbstractA very general and efficient catalytic protocol for the selective reduction of carboxylic acids to their corresponding alcohols under mild conditions is described. Various carboxylic acids, including benzoic acids, were reduced in good yields using the presented methodology. The ruthenium‐catalysed method yields a highly chemoselective reduction permitting the reduction of a carboxylic acid functionality in the presence of numerous other potentially reducible moieties.magnified image
• 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.
• Dye-sensitized photooxidation of silyl diazo compounds. Intramolecular oxygen transfer of carbonyl oxides
  作者：Akira Sekiguchi、Yoshio Kabe、Wataru Ando

  DOI：10.1021/jo00136a018

  日期：1982.7