(2-Methyl-1,5-dioxopentyl)methyldiphenylsilane | 162317-78-4

• 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: (2-Methyl-1,5-dioxopentyl)methyldiphenylsilane
• 英文别名: 4-Methyl-5-[methyl(diphenyl)silyl]-5-oxopentanal
• CAS: 162317-78-4
• 化学式: C₁₉H₂₂O₂Si
• 分子量: 310.468
• InChiKey: IKYYNGYAPZLHSM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2-Methyl-1,5-dioxopentyl)methyldiphenylsilane 在 吡啶 、 4-二甲氨基吡啶 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 生成 (1R*,5R*,8S*)-3-Acetoxy-2-(methoxycarbonyl)-8-methyl-5-(methyldiphenylsilyl)-9-oxabicyclo<3.3.1>non-2-ene
  参考文献：
  名称：

  Regioselectivity in [3 + 4] and [3 + 5] Annulation Reactions of Bis(trimethylsilyl) Enol Ethers with Acylsilane Dicarbonyl Dielectrophiles

  摘要：

  A number of 1,4- and 1,5-acylsilane dicarbonyl compounds were synthesized using Corey-Brook dithiane methods. These dicarbonyl substrates were annulated with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of TMSOTf, affording bicyclic ethers bearing silicon substituted at the bridgehead position: The annulation reactions proceeded with excellent regiochemical and good to excellent stereochemical control via a neighboring group participation mechanism. The silicon substituent was subsequently removed by treatment with fluoride ion. The overall transformation of annulation and desilylation represents a formal inversion of the regioselectivity normally exhibited with keto aldehyde dielectrophilic substrates in this process.

  DOI：

  10.1021/jo00106a025
• 作为产物：
  描述：

  (5,5-Dimethoxy-2-methyl-1-oxopentyl)methyldiphenylsilane dimethylhydrazone 在 amberlyst-15 resin 、 水 作用下， 以 丙酮 为溶剂， 反应 0.33h， 以41%的产率得到(2-Methyl-1,5-dioxopentyl)methyldiphenylsilane
  参考文献：
  名称：

  Regioselectivity in [3 + 4] and [3 + 5] Annulation Reactions of Bis(trimethylsilyl) Enol Ethers with Acylsilane Dicarbonyl Dielectrophiles

  摘要：

  A number of 1,4- and 1,5-acylsilane dicarbonyl compounds were synthesized using Corey-Brook dithiane methods. These dicarbonyl substrates were annulated with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of TMSOTf, affording bicyclic ethers bearing silicon substituted at the bridgehead position: The annulation reactions proceeded with excellent regiochemical and good to excellent stereochemical control via a neighboring group participation mechanism. The silicon substituent was subsequently removed by treatment with fluoride ion. The overall transformation of annulation and desilylation represents a formal inversion of the regioselectivity normally exhibited with keto aldehyde dielectrophilic substrates in this process.

  DOI：

  10.1021/jo00106a025

文献信息

• Regioselectivity in [3 + 4] and [3 + 5] Annulation Reactions of Bis(trimethylsilyl) Enol Ethers with Acylsilane Dicarbonyl Dielectrophiles
  作者：Gary A. Molander、Christopher S. Siedem

  DOI：10.1021/jo00106a025

  日期：1995.1

  A number of 1,4- and 1,5-acylsilane dicarbonyl compounds were synthesized using Corey-Brook dithiane methods. These dicarbonyl substrates were annulated with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of TMSOTf, affording bicyclic ethers bearing silicon substituted at the bridgehead position: The annulation reactions proceeded with excellent regiochemical and good to excellent stereochemical control via a neighboring group participation mechanism. The silicon substituent was subsequently removed by treatment with fluoride ion. The overall transformation of annulation and desilylation represents a formal inversion of the regioselectivity normally exhibited with keto aldehyde dielectrophilic substrates in this process.