(Z)-3-t-butyldimethylsilyl-4-cyclohexylbut-3-en-2-one | 1476045-32-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-3-t-butyldimethylsilyl-4-cyclohexylbut-3-en-2-one
• 英文别名: (Z)-3-[tert-butyl(dimethyl)silyl]-4-cyclohexylbut-3-en-2-one
• CAS: 1476045-32-5
• 化学式: C₁₆H₃₀OSi
• 分子量: 266.499
• InChiKey: SNBVZZDTBFOAQZ-QINSGFPZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.13
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  tert-butyldimethylsilylketene 在 三氟化硼乙醚 作用下， 以 二氯甲烷 、 氘代甲苯 、 甲苯 为溶剂， 反应 2.5h， 生成 (Z)-3-t-butyldimethylsilyl-4-cyclohexylbut-3-en-2-one
  参考文献：
  名称：

  Silicon Acceleration of a Tandem Alkene Isomerization/Electrocyclic Ring-opening of 2-Methyleneoxetanes to α,β-Unsaturated Methylketones

  摘要：

  The first rearrangement of 2-methyleneoxetanes to alpha,beta-unsaturated methylketones is reported. It is proposed that when these substrates are heated, the corresponding oxetenes are formed and subsequently undergo electrocyclic ring-opening to methyl vinylketones. In particular, alpha-silyl-alpha,beta-unsaturated methylketones were isolated in moderate to high yields and with high stereoselectivities. Based on the proposed mechanism, density functional theory explains the differential kinetics and stereoselectivities among substrates.

  DOI：

  10.1021/jo4014645

文献信息

• Silicon Acceleration of a Tandem Alkene Isomerization/Electrocyclic Ring-opening of 2-Methyleneoxetanes to α,β-Unsaturated Methylketones
  作者：Elisa Farber、Aleksandra Rudnitskaya、Santosh Keshipeddy、Kendricks S. Lao、José A. Gascón、Amy R. Howell

  DOI：10.1021/jo4014645

  日期：2013.11.15

  The first rearrangement of 2-methyleneoxetanes to alpha,beta-unsaturated methylketones is reported. It is proposed that when these substrates are heated, the corresponding oxetenes are formed and subsequently undergo electrocyclic ring-opening to methyl vinylketones. In particular, alpha-silyl-alpha,beta-unsaturated methylketones were isolated in moderate to high yields and with high stereoselectivities. Based on the proposed mechanism, density functional theory explains the differential kinetics and stereoselectivities among substrates.