Tert-butyl-(4-tert-butyl-3-methoxydioxetan-3-yl)oxy-dimethylsilane | 134736-29-1

• 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: Tert-butyl-(4-tert-butyl-3-methoxydioxetan-3-yl)oxy-dimethylsilane
• 英文别名: tert-butyl-(4-tert-butyl-3-methoxydioxetan-3-yl)oxy-dimethylsilane
• CAS: 134736-29-1
• 化学式: C₁₃H₂₈O₄Si
• 分子量: 276.448
• InChiKey: RKUOWLPMNXVJLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Tert-butyl-(4-tert-butyl-3-methoxydioxetan-3-yl)oxy-dimethylsilane 以 四氯化碳 为溶剂， 生成 [Tert-butyl(dimethyl)silyl] methyl carbonate 、 Methyl 2-[[(1,1-dimethylethyl)dimethylsilyl]dioxy]-3,3-dimethylbutanoate 、 特戊醛
  参考文献：
  名称：

  Photooxygenation of silyl ketene acetals: dioxetanes as precursors to .alpha.-silylperoxy esters in the silatropic ene reaction

  摘要：

  Photooxygenation of silyl ketene acetals afforded dioxetanes, which subsequently underwent secondary reactions to give rearrangement products (alpha-silylperoxy esters, major products) and cleavage products (pivalaldehyde, minor product). The kinetics of these reactions were studied by NMR and chemiluminescence. The activation energy of the chemiluminescent cleavage process was 2-3 kcal/mol higher than that of the rearrangement. In the presence of catalytic amounts of CF3COCF3 or CF3COCH3, the (E)-silyl ketene acetals rearranged into their Z isomers. Photooxygenation of the (E)- and (Z)-silyl ketene acetals showed that the [2 + 2] cycloaddition was rigorously diastereoselective. Trapping experiments with acetaldehyde confirmed the intermediacy of 1,4-zwitterions in the rearrangement of the (E)- and (Z)-dioxetanes into alpha-silylperoxy esters, but such intermediates were not detected during the photooxygenation of the silyl ketene acetals; the latter proceeds presumably via perepoxides.

  DOI：

  10.1021/jo00015a030
• 作为产物：
  描述：

  (Z)-tert-Butylketene Methyl tert-Butyldimethylsilyl Acetal 在 氧气 、 tetraphenylporphyrin 作用下， 以 四氯化碳 为溶剂， 反应 0.67h， 生成 Tert-butyl-(4-tert-butyl-3-methoxydioxetan-3-yl)oxy-dimethylsilane
  参考文献：
  名称：

  Photooxygenation of silyl ketene acetals: dioxetanes as precursors to .alpha.-silylperoxy esters in the silatropic ene reaction

  摘要：

  Photooxygenation of silyl ketene acetals afforded dioxetanes, which subsequently underwent secondary reactions to give rearrangement products (alpha-silylperoxy esters, major products) and cleavage products (pivalaldehyde, minor product). The kinetics of these reactions were studied by NMR and chemiluminescence. The activation energy of the chemiluminescent cleavage process was 2-3 kcal/mol higher than that of the rearrangement. In the presence of catalytic amounts of CF3COCF3 or CF3COCH3, the (E)-silyl ketene acetals rearranged into their Z isomers. Photooxygenation of the (E)- and (Z)-silyl ketene acetals showed that the [2 + 2] cycloaddition was rigorously diastereoselective. Trapping experiments with acetaldehyde confirmed the intermediacy of 1,4-zwitterions in the rearrangement of the (E)- and (Z)-dioxetanes into alpha-silylperoxy esters, but such intermediates were not detected during the photooxygenation of the silyl ketene acetals; the latter proceeds presumably via perepoxides.

  DOI：

  10.1021/jo00015a030

文献信息

• Photooxygenation of silyl ketene acetals: dioxetanes as precursors to .alpha.-silylperoxy esters in the silatropic ene reaction
  作者：Waldemar Adam、Xiaoheng Wang

  DOI：10.1021/jo00015a030

  日期：1991.7

  Photooxygenation of silyl ketene acetals afforded dioxetanes, which subsequently underwent secondary reactions to give rearrangement products (alpha-silylperoxy esters, major products) and cleavage products (pivalaldehyde, minor product). The kinetics of these reactions were studied by NMR and chemiluminescence. The activation energy of the chemiluminescent cleavage process was 2-3 kcal/mol higher than that of the rearrangement. In the presence of catalytic amounts of CF3COCF3 or CF3COCH3, the (E)-silyl ketene acetals rearranged into their Z isomers. Photooxygenation of the (E)- and (Z)-silyl ketene acetals showed that the [2 + 2] cycloaddition was rigorously diastereoselective. Trapping experiments with acetaldehyde confirmed the intermediacy of 1,4-zwitterions in the rearrangement of the (E)- and (Z)-dioxetanes into alpha-silylperoxy esters, but such intermediates were not detected during the photooxygenation of the silyl ketene acetals; the latter proceeds presumably via perepoxides.