3-(trimethylsilyl)-1-<(trimethylsilyl)oxy>-1-cyclohexene | 55942-21-7

• 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: 3-(trimethylsilyl)-1-<(trimethylsilyl)oxy>-1-cyclohexene
• 英文别名: 3-trimethylsilyl-1-cyclo-hexenyl trimethylsilyl ether；3-(trimethylsilyl)-1-[(trimethylsilyl)oxy]-1-cyclohexene；Trimethyl-(3-trimethylsilylcyclohexen-1-yl)oxysilane
• CAS: 55942-21-7
• 化学式: C₁₂H₂₆OSi₂
• 分子量: 242.509
• InChiKey: ZNRNJCODRTUMBW-UHFFFAOYSA-N

物化性质

• 沸点：
  245.1±40.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.61
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(trimethylsilyl)-1-<(trimethylsilyl)oxy>-1-cyclohexene 生成 3-trimethylsilylcyclohexan-1-one
  参考文献：
  名称：

  Nouvelle methode de C-silylation directe de cetones saturees ou α-ethyleniques

  摘要：

  DOI：

  10.1016/s0022-328x(00)91282-8
• 作为产物：
  描述：

  三甲基氯硅烷 、 2-环己烯-1-酮 在 lithium silvers 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 3-(trimethylsilyl)-1-<(trimethylsilyl)oxy>-1-cyclohexene
  参考文献：
  名称：

  Concerning the formation, reduction and conformations of .beta.-(trimethylsilyl)- and .beta.-(trimethylstannyl)cyclohexanones

  摘要：

  DOI：

  10.1021/jo00140a048

文献信息

• Copper and silicon mediated, HMPA-free, n+3 ring expansions for the construction of medium sized lactones and lactams: short synthesis of (+)-cis-lauthisan
  作者：Gary H. Posner、Mark A. Hatcher、William A. Maio

  DOI：10.1016/j.tet.2016.05.063

  日期：2016.10

  enolates for the construction, after oxidative fragmentation, of ring expanded lactones, n+3 atoms in size. Importantly, azido lactones were found to be valuable in an extension of this protocol involving the n+3+p expansion into a series of hydroxyolefinic lactams. We also document a short, stereoselective total synthesis of (+)-cis-lauthisan and a new, cuprate-mediated and HMPA-free procedure for the generation

  在本报告中，几个新的环氧化物实例与β-甲硅烷基酮烯酸酯结合在一起，用于氧化断裂后构造n + 3原子大小的扩环内酯。重要的是，发现叠氮基内酯在该方案的扩展中很有价值，该扩展方案涉及将n + 3 + p扩展成一系列羟基烯烃内酰胺。我们还记录了（+）-顺式-lauthisan的短时，立体选择性全合成以及生成β-硅烷基甲硅烷基醚的新型，无铜酸盐介导且无HMPA的程序，可用于环境友好的中型内酯的构建。
• New silicon-mediated ring expansion of n-sized conjugated cycloalkenones into homoallylic n+3 lactones
  作者：Mark A. Hatcher、Kristina Borstnik、Gary H. Posner

  DOI：10.1016/s0040-4039(03)01308-x

  日期：2003.7

  diverse epoxides and BF3·OEt2, produces useful γ-lactols and γ-hydroxyketones. Hypervalent iodine-promoted oxidative fragmentation then yields regiospecifically unsaturated, 3-atom ring expanded, 8–10 membered homoallylic lactones with good control of alkene geometry.

  硅亲核性β-加成到各种2-环烯酮中，然后最终使用各种环氧化物和BF 3 ·OEt 2对相应的环烷酮烯醇化物进行温和快速的α-烷基化反应，生成有用的γ-内酯和γ-羟基酮。然后，高价碘促进的氧化裂解产生区域特异性的不饱和，3原子环膨胀，8-10元的均烯丙基内酯，并能很好地控制烯烃的几何形状。
• Silicon-Induced Ene-Type Reaction in the Thermal Conversion of Enolates to β-Silyl Enones with Molecular Dioxygen
  作者：Jih Ru Hwu、Chien Hsien Chen、Chuan-I Hsu、Asish R. Das、Yen Cheng Li、Lung Ching Lin

  DOI：10.1021/ol800007v

  日期：2008.5.1

  Reaction of alkyl, acetoxy, and silyl enol ethers of 3-(organosilyl)cyclohexanone with molecular dioxygen in toluene at 110 degrees C produced the corresponding conjugated enones in yields up to 88% yield. The reaction of the same type failed on replacement of the silyl group at the C-3 position with an isopropyl group. These results indicate the existence of an unprecedented silicon-induced ene-type reaction. Its reaction mechanism, generality, limitations, and exceptions are discussed.
• New Silicon-Mediated, Sequential Ring Expansions of <i>n</i>-Sized 2-Cycloalkenones into Hydroxyolefinic <i>n</i> + <i>m</i> + <i>p</i> Medium-Sized Lactones:  Short Synthesis of (−)-Phoracantholide-J
  作者：Gary H. Posner、Mark A. Hatcher、William A. Maio

  DOI：10.1021/ol051854x

  日期：2005.9.1

  In only four steps from 2-cyclopentenone and 2-cyclohexenone, sequential three- or four-atom and then one- to three-atom ring enlargements produce nine- to 12-membered hydroxyolefinic lactones on a gram scale. 2-Cyclopentenone undergoes this serial 5 + 3 + 2 process to form 10-membered ring natural (-)-phoracantholide-J in six linear steps and 26% overall yield.
• Preparation of bicyclo[5.3.0]decan-1-ols from the tandem anionic oxy-Cope rearrangement/allylsilane cyclization of 1,2-divinylcyclohexanols
  作者：Jisheng Li、Teresa Gallardo、James B. White

  DOI：10.1021/jo00307a003

  日期：1990.9