<2-(4-Oxobutyl)-1,3-dithian-2-yl>methyldiphenylsilane | 162318-12-9

• 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-(4-Oxobutyl)-1,3-dithian-2-yl>methyldiphenylsilane
• 英文别名: 4-[1-(methyl-diphenyl-silyl)-2,6-dithiacyclohexyl]-butanal；1,3-Dithiane-2-butanal, 2-(methyldiphenylsilyl)-；4-[2-[methyl(diphenyl)silyl]-1,3-dithian-2-yl]butanal
• CAS: 162318-12-9
• 化学式: C₂₁H₂₆OS₂Si
• 分子量: 386.654
• InChiKey: UBCLMUQSCAENGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.35
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  <2-(4-Oxobutyl)-1,3-dithian-2-yl>methyldiphenylsilane 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 以65%的产率得到(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
• 作为产物：
  描述：

  甲基二苯基氯硅烷 在 盐酸 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 7.0h， 生成 <2-(4-Oxobutyl)-1,3-dithian-2-yl>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

• Intramolecular cyclizations of α-stannyl radicals to acylsilanes: regiospecific syntheses of five-membered cyclic silyl enol ethers
  作者：Yeun-Min Tsai、Sheng-Yueh Chang

  DOI：10.1039/c39950000981

  日期：——

  α-Stannyl radicals generated from acylsilanes 5, 13 and 14 cyclize to give good yields of cyclic silyl enol ethers after sequential cyclizations, radical Brook rearrangements and β-scissions.

  从acylsilanes产生α-甲锡烷基的基团5，13和14环化，得到良好收率的环状甲硅烷基烯醇醚顺序环化后，自由基布鲁克重排和β-链断裂。
• The Application of Intramolecular Radical Cyclizations of Acylsilanes in the Regiospecific Formation of Cyclic Silyl Enol Ethers
  作者：Chih-Hao Huang、Sheng-Yueh Chang、Nung-Sen Wang、Yeun-Min Tsai

  DOI：10.1021/jo010883s

  日期：2001.12.1

  terminal alpha-stannyl bromide or xanthate functionalities are prepared. Alpha-stannyl radicals generated from these acylsilanes undergo intramolecular cyclizations to give cyclic silyl enol ethers regiospecifically. The radical processes involve radical cyclization, Brook rearrangement, and beta-fragmentation in sequence. A tributylstannyl group serves as the radical leaving group. The newly formed

  制备具有末端α-锡烷基溴或黄原酸酯官能团的酰基硅烷。由这些酰基硅烷产生的α-锡烷基自由基进行分子内环化，以区域特异性地产生环状甲硅烷基烯醇醚。自由基过程依次涉及自由基环化，布鲁克重排和β片段化。三丁基锡烷基用作自由基离去基团。新形成的sigma键和pi键位于相同的两个碳原子之间。这种方法仅限于五元环的形成。在另一种途径中，合成了ω-溴-α-苯基磺酰甲硅烷基硅烷。这些α-磺酰基甲硅烷基硅烷的自由基环化还产生环状甲硅烷基烯醇醚。苯磺酰基部分是该系统中的自由基离去基团。此外，新形成的sigma键和pi键位于共享一个碳原子的相邻位置。后一种方法对于五元和六元环形成均有效。
• 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.