hexanoyl-tert-butyldimethylsilane | 144968-87-6

• 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: hexanoyl-tert-butyldimethylsilane
• 英文别名: 1-[Tert-butyl(dimethyl)silyl]hexan-1-one
• CAS: 144968-87-6
• 化学式: C₁₂H₂₆OSi
• 分子量: 214.423
• InChiKey: UFAFDCQLYPCHGH-UHFFFAOYSA-N

物化性质

• 沸点：
  216.6±8.0 °C(Predicted)
• 密度：
  0.826±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  hexanoyl-tert-butyldimethylsilane 在 甲基锂 、 lithium bromide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.17h， 生成 (E)-2-Fluoro-1-(perfluorobutyl)-1-piperidinooct-1-en-3-one
  参考文献：
  名称：

  Mixed organofluorine-organosilicon chemistry. 4. Perfluoroenoxysilanes: synthesis and reactivity

  摘要：

  1-Alkyl (or aryl)-1-[(trialkylsilyl)oxy]perfluoroalk-1-enes were synthesized from acylsilanes and perfluoroalkyl iodides. Perfluoroorganolithium and magnesium were used for aliphatic and aromatic derivatives, respectively. These enoxysilanes have nucleophilic as well as electrophilic properties. They are enolate equivalents, leading to 2-hydroperfluoroalkyl ketones on hydrolysis, or aldol products. With good nucleophiles like amines, they react as electron poor alkenes to give beta-enamino ketones.

  DOI：

  10.1021/jo00076a029
• 作为产物：
  描述：

  2-(叔丁基二甲基甲硅烷基)-1,3-二噻烷 在 正丁基锂 、 偶氮二异丁腈 、 Celite 、 三氟化硼乙醚 、 三正丁基氢锡 、 mercury(II) oxide 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 hexanoyl-tert-butyldimethylsilane
  参考文献：
  名称：

  The Scope and Limitations of Intramolecular Radical Cyclizations of Acylsilanes with Alkyl, Aryl, and Vinyl Radicals

  摘要：

  5-Exo cyclizations of primary and secondary radicals with acylsilanes successfully give cyclopentyl silyl ethers. The corresponding 6-exo cyclizations are sensitive to changes of the size of silyl groups. Secondary radicals undergo 6-exo cyclizations with acylsilanes more slowly. Reaction of aryl radical with acylsilane proceeds well for 5-exo cyclization but not for 6-exo cyclization. Vinyl radicals give best results in 5-exo cyclizations with acylsilanes but give low yields (similar to 30%) in 6-exo cyclizations. Intramolecular cyclizations of vinyl radicals with acylsilanes give enol silyl ethers regiospecifically.

  DOI：

  10.1021/jo9711302

文献信息

• Mixed Organofluorine-Organosilicon Chemistry; 2. Synthesis of Alkyl and Aryl Perfluoroalkyl Trialkylsilyl Carbinols
  作者：Boniface Dondy、Pascale Doussot、Charles Portella

  DOI：10.1055/s-1992-26287

  日期：——

  1-Alkyl- and 1-aryl-1-trialkylsilyl-1-perfluoroalkanols, a new class of alcohols, were synthesized from acyl or aroylsilanes and perfluoroorganomagnesium reagents, and their spectroscopic characteristics are described.

  1-烷基和1-芳基-1-三烷基硅烷-1-全氟烷醇是一类新型醇化合物，通过酰基或芳酰基硅烷与全氟有机镁试剂合成，并描述了它们的光谱特征。
• Radical cyclizations of bromo acylsilanes and intramolecular trapping of the rearranged α-silyloxy radicals
  作者：Yeun-Min Tsai、Kuo-Hsiang Tang、Weir-Torn Jiaang

  DOI：10.1016/s0040-4039(00)91780-5

  日期：1993.2

  Radical 1,5-exo cyclizations of acylsilanes involving secondary radicals are quite effective. In contrast, 1,6-exo cyclizations are more sensitive toward steric effect. Tandem radical cyclization process can be designed.
• Asymmetric Hydrogenation of Aromatic, Aliphatic, and α,β-Unsaturated Acyl Silanes Catalyzed by Tol-binap/Pica Ruthenium(II) Complexes: Practical Synthesis of Optically Active α-Hydroxysilanes
  作者：Noriyoshi Arai、Ken Suzuki、Satoshi Sugizaki、Hiroko Sorimachi、Takeshi Ohkuma

  DOI：10.1002/anie.200704696

  日期：2008.2.15
• The Scope and Limitations of Intramolecular Radical Cyclizations of Acylsilanes with Alkyl, Aryl, and Vinyl Radicals
  作者：Sheng-Yueh Chang、Weir-Torn Jiaang、Chaur-Donp Cherng、Kuo-Hsiang Tang、Chih-Hao Huang、Yeun-Min Tsai

  DOI：10.1021/jo9711302

  日期：1997.12.1

  5-Exo cyclizations of primary and secondary radicals with acylsilanes successfully give cyclopentyl silyl ethers. The corresponding 6-exo cyclizations are sensitive to changes of the size of silyl groups. Secondary radicals undergo 6-exo cyclizations with acylsilanes more slowly. Reaction of aryl radical with acylsilane proceeds well for 5-exo cyclization but not for 6-exo cyclization. Vinyl radicals give best results in 5-exo cyclizations with acylsilanes but give low yields (similar to 30%) in 6-exo cyclizations. Intramolecular cyclizations of vinyl radicals with acylsilanes give enol silyl ethers regiospecifically.
• Mixed organofluorine-organosilicon chemistry. 4. Perfluoroenoxysilanes: synthesis and reactivity
  作者：Pascale Doussot、Charles Portella

  DOI：10.1021/jo00076a029

  日期：1993.11

  1-Alkyl (or aryl)-1-[(trialkylsilyl)oxy]perfluoroalk-1-enes were synthesized from acylsilanes and perfluoroalkyl iodides. Perfluoroorganolithium and magnesium were used for aliphatic and aromatic derivatives, respectively. These enoxysilanes have nucleophilic as well as electrophilic properties. They are enolate equivalents, leading to 2-hydroperfluoroalkyl ketones on hydrolysis, or aldol products. With good nucleophiles like amines, they react as electron poor alkenes to give beta-enamino ketones.