N-methyl-N-((trimethylsilyl)oxy)acetamide | 1327239-54-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: N-methyl-N-((trimethylsilyl)oxy)acetamide
• 英文别名: N-methyl-N-(trimethylsilyloxy)acetamide
• CAS: 1327239-54-2
• 化学式: C₆H₁₅NO₂Si
• 分子量: 161.276
• InChiKey: ZIVAUMNLOMLUIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.23
• 重原子数：
  10.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  29.54
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  N-methyl-N-((trimethylsilyl)oxy)acetamide 、 苯基三氟硼酸钾 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 2-fluoro-4,5-dimethyl-2-phenyl-1,3,4,2-dioxazaborol-4-ium-2-uide
  参考文献：
  名称：

  Expanded Substrate Scope and Improved Reactivity of Ether-Forming Cross-Coupling Reactions of Organotrifluoroborates and Acetals

  摘要：

  Mixed acetals and organotrifluoroborates undergo BF3 center dot OEt2-promoted cross-couplings to give dialkyl ethers under simple, mild conditions. A survey of reaction partners identified a hydroxamate leaving group that improves the regioselectivity and product yield in the BF3 center dot OEt2-promoted coupling reaction of mixed acetals and potassium alkynyl-, alkenyl-, aryl- and heteroaryltrifluoroborates to access substituted dialkyl ethers. This leaving group enables the reaction to proceed rapidly under mild conditions (0 degrees C, 5-60 min) and permits reactions with electron-deficient potassium aryltrifluoroborates that are less reactive with other acetal substrates. A study of the reaction mechanism and characterization of key intermediates by NMR spectroscopy and X-ray crystallography identified a role for the hydroxamate moiety as a reversible leaving group that serves to stabilize the key oxocarbenium intermediate and the need for a slight excess of organodifluoroborane to serve as a catalyst. A secondary role for the boron nucleophile as an activating ligand was also considered. These studies provide the basis for a general class of reagents that lead to dialkyl ethers by a simple, predictable cross-coupling reaction.

  DOI：

  10.1021/ja205174c
• 作为产物：
  描述：

  N-甲基乙酰氧肟酸 、 六甲基二硅氮烷 以 四氢呋喃 为溶剂， 反应 2.0h， 以77%的产率得到N-methyl-N-((trimethylsilyl)oxy)acetamide
  参考文献：
  名称：

  Expanded Substrate Scope and Improved Reactivity of Ether-Forming Cross-Coupling Reactions of Organotrifluoroborates and Acetals

  摘要：

  Mixed acetals and organotrifluoroborates undergo BF3 center dot OEt2-promoted cross-couplings to give dialkyl ethers under simple, mild conditions. A survey of reaction partners identified a hydroxamate leaving group that improves the regioselectivity and product yield in the BF3 center dot OEt2-promoted coupling reaction of mixed acetals and potassium alkynyl-, alkenyl-, aryl- and heteroaryltrifluoroborates to access substituted dialkyl ethers. This leaving group enables the reaction to proceed rapidly under mild conditions (0 degrees C, 5-60 min) and permits reactions with electron-deficient potassium aryltrifluoroborates that are less reactive with other acetal substrates. A study of the reaction mechanism and characterization of key intermediates by NMR spectroscopy and X-ray crystallography identified a role for the hydroxamate moiety as a reversible leaving group that serves to stabilize the key oxocarbenium intermediate and the need for a slight excess of organodifluoroborane to serve as a catalyst. A secondary role for the boron nucleophile as an activating ligand was also considered. These studies provide the basis for a general class of reagents that lead to dialkyl ethers by a simple, predictable cross-coupling reaction.

  DOI：

  10.1021/ja205174c