benzyl 2-(dimethyl(phenyl)silyl)-2-oxoacetate | 443988-56-5

• 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: benzyl 2-(dimethyl(phenyl)silyl)-2-oxoacetate
• 英文别名: Benzyl 2-[dimethyl(phenyl)silyl]-2-oxoacetate
• CAS: 443988-56-5
• 化学式: C₁₇H₁₈O₃Si
• 分子量: 298.414
• InChiKey: VQWPBLKOLXDUJD-UHFFFAOYSA-N

物化性质

• 沸点：
  387.7±35.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.45
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  benzyl 2-(dimethyl(phenyl)silyl)-2-oxoacetate 在 sodium carbonate 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  Synthesis of novel silylated 1,2,4-triazin-5-ones

  摘要：

  The reaction of various alpha-silyl-alpha-keto esters with thiosemicarbazide at 50 degrees C in ethyl acetate was found to give alpha-silyl-substituted thiosemicarbazone-acetic acid esters in good yield. These may then be converted to their corresponding silyl-substituted 1,2,4-triazin-5-ones by cyclization under basic conditions. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.04.021
• 作为产物：
  描述：

  benzyl 2-dimethyl(phenyl)silyl-2-diazoacetate 在 dirhodium tetraacetate 、 methyloxirane 作用下， 以 甲苯 为溶剂， 以85%的产率得到benzyl 2-(dimethyl(phenyl)silyl)-2-oxoacetate
  参考文献：
  名称：

  Synthesis and Use of α-Silyl-Substituted α-Hydroxyacetic Acids

  摘要：

  Rhodium-catalyzed oxygen transfer was used to generate benzyl 2-sifyi-2-oxoacetates in good yields. The hydrogenation of these compounds led to chiral alpha-silyl-substituted a-hydroxyacetic acids. Resolution by means of HPLC using a chiral stationary phase afforded an enantiomerically pure representative of this class of compounds, which was successfully applied as a chiral ligand in an asymmetric aldol-type reaction.

  DOI：

  10.1021/ol025911n

文献信息

• Catalytic asymmetric addition of thiols to silyl glyoxylates for synthesis of multi-hetero-atom substituted carbon stereocenters
  作者：Mingming Guan、Shiyu Wang、Yao Luo、Weidi Cao、Xiaohua Liu、Xiaoming Feng

  DOI：10.1039/d1sc01096d

  日期：——

  A chiral Lewis acid-catalyzed enantioselective addition of thiols to silyl glyoxylates was developed. The reaction proceeds well with a broad range of thiols and acylsilanes, affording the target tertiary chiral α-silyl–α-sulfydryl alcohols with multi-hetero-atom carbon stereocenters in excellent yields (up to 99%) and enantioselectivities (up to 98% ee). A series of control experiments were conducted

  开发了手性路易斯酸催化的巯基对乙氧基化甲硅烷基化物的对映选择性加成。反应可与多种硫醇和酰基硅烷一起进行，使目标叔级手性α-甲硅烷基-α-巯基醇与多杂原子碳立构中心形成，并具有出色的收率（高达99％）和对映选择性（高达98％） ee）。进行了一系列对照实验以阐明反应机理。
• Bimetallic tandem catalysis-enabled enantioselective cycloisomerization/carbonyl–ene reaction for construction of 5-oxazoylmethyl α-silyl alcohol
  作者：Xinpeng Sang、Yuhao Mo、Shiya Li、Xiaohua Liu、Weidi Cao、Xiaoming Feng

  DOI：10.1039/d3sc01048a

  日期：——

  A bimetallic tandem catalysis-enabled enantioselective cycloisomerization/carbonyl–ene reaction was developed. The reaction proceeded well with a broad range of N-propargylamides and acylsilanes, affording the target chiral 5-oxazoylmethyl α-silyl alcohols in up to 95% yield and 99% ee under mild conditions. Importantly, this facile protocol was available for the late-stage modification of several

  开发了一种双金属串联催化的对映选择性环异构化/羰基-烯反应。该反应与多种N-炔丙基酰胺和酰基硅烷一起顺利进行，在温和条件下以高达 95% 的产率和 99% ee 得到目标手性 5-恶唑酰基甲基 α-硅醇。重要的是，这种简便的方案可用于几种生物活性分子的后期修饰。基于机理研究和控制实验，提出了可能的催化循环和过渡态来阐明反应过程和对映诱导。